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398 Select bibliography

WENIRUP, C . Reactive Molecules: The Neutral Reactive Intermediate in Organic Chemistry (Wiley, 1984).

Review series Advances in Physical Organic Chemistry. WLD, v. and B-, D.

(Eds) (Academic Press, Vol. I, 1963- ). Organic Reaction Mechanisms. KNIPE, A. C . and W A ~ , W. E. (Eds)

(Interscience, Vol. I, 1966- ). Progress in Physical Organic Chemistry. TAFT, R. W. (Ed.) (Inter-

science, Vol. 1, 1963- ). Reactive Intermediates-A Serial Publication, JONES, M. and MOSS, R.

A. (Eds) (Wiley-Interscience, Vol. I, 1978- ).

Audio cassettes

The following titles in the 'Chemistry Cassette' series are published by, and are available from, The Chemical Society, Blackhorse Road, Letchworth, Herts., SG6 lHN, England: CC3 S W , P. Some Organic Reaction Pathways: ( A ) . Eliminatibn;

( B ) . Aromatic Substitution (1975). CC6 S W , P. Some Reaction Pathways of Double Bonds: ( A ) .

C=C; ( B ) . C=O (1977). CC7 S W , P. Some Reaction Pathways of Carboxylic Acid Denva-

tives (1979). CC9 S-, P. Radicals and their Reaction Pathways (1979). CC11 SYKES, P. Linear Free Energy Relationships (1980).

Index

Aeetals cyclic, 210 formation, 209,289 hydrolysis, 74,210

Acid catalysis general, 74 specific, 74

AA,l pathway, 242,243 AA,2 pathway, 241,244,384 A,? pathway, 241 Aad~ty

anion stability and, 23,55,271 aromaticity and, 275 Br0nsted and, 53 constant K,, 54,271 definitions of, 53 A G ~ and, 58,60,61, 394 AW and, 58,394 Ase and, 58,394 effect of solvent, 56 effect of temperature, 64 H-bonding in, 63,64 hybridisation and, 59,273 in C-H comps., 251,270 kinetic control of, 270,280 Lewis and, 54 origin in organic comps., 55 steric effects in, 58

Acid strength alcohols, 55, 56 aliphatic acids, 54, 55, 57, 59 alkanes, 55,271 alkenes, 272 alkynes, 223,273,289,294 aromatic acids, 62 catalysis and, 74 dicarboxylic acids, 63 imides, 68 nitroalkanes, 272,280,283 phenols, 23, 56,61 triphenylmethane, 271

Acrylonitrile, 199 Activated complex, 38

Activation parameters energy, E,, 38 enthalpy, AH+, 38 entropy, AS*, 39 free energy, AG*, 38

Acyl cations, 102, 144,240,242, 379 Acyloin condensation, 218 Addition, 30

1,3-dipolar, 192, 194,351 electrophilic, 31, 50, 178-198 nucleophilic, 31, 198, 207-245 radical, 31,313-323 to +C, 31,51, 103, 113, 178, 188 to (+C, 182 to -+C, 195 to ckc-c==O, 200 to e N , 244 to C+0, 31,50, 103,203

Adsorption, 191 Aldehyde ammonias, 220 Aldol reaction, 224

acid catalysed, 225 crossed, 226 intramolecular, 226 reversibility, 75, 224

Alkenes cycloaddition, 348

polar addition, 178-195 protection in, 265 radical addition, 313-323 relative stability, 26,256

Alkylchlorosulphites, decomp.. 93 Alkyl shifts, 111, 113, 115,293,337 Alkynes

acidity, 223,272 addition to -0,223 alkylation, 289 dimerisation, 294 ozonolysis, 194

cation, 85, 105, 196 radical, 311 rearrangement, 109

398 Select bibliography

WENIRUP, C . Reactive Molecules: The Neutral Reactive Intermediate in Organic Chemistry (Wiley, 1984).

Review series Advances in Physical Organic Chemistry. WLD, v. and B-, D.

(Eds) (Academic Press, Vol. I, 1963- ). Organic Reaction Mechanisms. KNIPE, A. C . and W A ~ , W. E. (Eds)

(Interscience, Vol. I, 1966- ). Progress in Physical Organic Chemistry. TAFT, R. W. (Ed.) (Inter-

science, Vol. 1, 1963- ). Reactive Intermediates-A Serial Publication, JONES, M. and MOSS, R.

A. (Eds) (Wiley-Interscience, Vol. I, 1978- ).

Audio cassettes

The following titles in the 'Chemistry Cassette' series are published by, and are available from, The Chemical Society, Blackhorse Road, Letchworth, Herts., SG6 lHN, England: CC3 S W , P. Some Organic Reaction Pathways: ( A ) . Eliminatibn;

( B ) . Aromatic Substitution (1975). CC6 S W , P. Some Reaction Pathways of Double Bonds: ( A ) .

C=C; ( B ) . C=O (1977). CC7 S W , P. Some Reaction Pathways of Carboxylic Acid Denva-

tives (1979). CC9 S-, P. Radicals and their Reaction Pathways (1979). CC11 SYKES, P. Linear Free Energy Relationships (1980).

Index

Aeetals cyclic, 210 formation, 209,289 hydrolysis, 74,210

Acid catalysis general, 74 specific, 74

AA,l pathway, 242,243 AA,2 pathway, 241,244,384 A,? pathway, 241 Aad~ty

anion stability and, 23,55,271 aromaticity and, 275 Br0nsted and, 53 constant K,, 54,271 definitions of, 53 A G ~ and, 58,60,61, 394 AW and, 58,394 Ase and, 58,394 effect of solvent, 56 effect of temperature, 64 H-bonding in, 63,64 hybridisation and, 59,273 in C-H comps., 251,270 kinetic control of, 270,280 Lewis and, 54 origin in organic comps., 55 steric effects in, 58

Acid strength alcohols, 55, 56 aliphatic acids, 54, 55, 57, 59 alkanes, 55,271 alkenes, 272 alkynes, 223,273,289,294 aromatic acids, 62 catalysis and, 74 dicarboxylic acids, 63 imides, 68 nitroalkanes, 272,280,283 phenols, 23, 56,61 triphenylmethane, 271

Acrylonitrile, 199 Activated complex, 38

Activation parameters energy, E,, 38 enthalpy, AH+, 38 entropy, AS*, 39 free energy, AG*, 38

Acyl cations, 102, 144,240,242, 379 Acyloin condensation, 218 Addition, 30

1,3-dipolar, 192, 194,351 electrophilic, 31, 50, 178-198 nucleophilic, 31, 198, 207-245 radical, 31,313-323 to +C, 31,51, 103, 113, 178, 188 to (+C, 182 to -+C, 195 to ckc-c==O, 200 to e N , 244 to C+0, 31,50, 103,203

Adsorption, 191 Aldehyde ammonias, 220 Aldol reaction, 224

acid catalysed, 225 crossed, 226 intramolecular, 226 reversibility, 75, 224

Alkenes cycloaddition, 348

polar addition, 178-195 protection in, 265 radical addition, 313-323 relative stability, 26,256

Alkylchlorosulphites, decomp.. 93 Alkyl shifts, 111, 113, 115,293,337 Alkynes

acidity, 223,272 addition to -0,223 alkylation, 289 dimerisation, 294 ozonolysis, 194

cation, 85, 105, 196 radical, 311 rearrangement, 109

400 Index

Ambident nucleophiles, 97 Amides

from Beckmann, 123 Hofmann reaction, 49, 122 hydrolysis, 239,245, 388 reduction, 214

Amidines basicity, 69 formation, 244

Aminoazo comps, 148 Anionic polymerisation, 200,226 Antarafacial shifts, 353 Anthracene, 17

photodimer, 337 transannular peroxide, 331

Anti-bonding orbitals, 6, 292 Anti-knock agents, 305 Anti-Markownikov addition, 317 Anti-oxidants, 330 Antiperiplanar conformation, 118,253 Arenium ions, 131 Arenonium ions, 131 Arndt-Eistert reaction, 119 Aromaticity, l4

cycloheptatrienyl cation, 18, 104, 106 cyclopentadienyl anion, 18, 275 cyclopropenyl cation, 18, 106 n.m.r. spectrum and, 18 requirements for, 17

Aromatic substitution, 41 electrophilic, 130-167 internal, 334, 381 nucleophilic, 167-177 radical, 331-335

Arrhenius equation, 38 Arrows

curved, l9 double-headed, 19

Arylation, 332 Aryne intermediates, 21, 174 Associative process, 239, 241 Atactic polymers, 322 Atomic orbitals, 1, 342 Aufbau principle, 3 Autoxidation, 306, 318,328

alkenes, 329 benzaldehyde, 306,330 cumene, l28 ethers, 329 tetralin, 329

Axial overlap, 6 h ides , 123, 194 Azoalkanes

photolysis, 304 thermolysis, 305

BAc2 pathway, 239,384 Baeyer-Villiger oxidation, 127 Barton reaction, 337 Base catalysis

general, 75 ion exchange resins, 226 specific, 75

Basicity aromaticity and, 69,72 Brensted and, 53 cation stability and, 67, 68, 72, 73 constant, 65 effect of solvent on, 66,67 H-bonding in, 67 inductive effect and, 22,66 Lewis and, 54 multiply bonded N and, 72 nucleophilicity and, 96 origin in organic comps., 66 ortho effects in, 71 softness, 96 steric effects in, 70,71

Basic strength aliphatic amines, 66 amides, 68 amidines, 69 aromatic bases, 69 catalysis and, 75 conjugate acids, 65 AP and, 66 guanidine, 68 heterocyclic bases, 72, 166 t e t r a a k y h m m ~ ~ ~ m hydroxides, 67

Beckmann rearrangement, 123 acid catalysis, 124 ~,'80 in, 125 intramolecularity, 126 solvent polarity and, 126 stereoselectivity, 124

Benzene aromaticity and, 14 bond lengths, 15 charge cloud, 15, 130 delocalisation in, 14, 130 heat of hydrogenation, 16 KekulC structures, 14, 194 m.0.s of, 14 n.m.r. signal, 18 ozonolysis, 194 planarity, 14 stability, 15

Benzilic acid rearrangement, 232 Benzoin condensation, 231

cyanide ion in, 231 thiazolium ylids in, 232

Benzotriazoles, 148, 176 Benzyne, 175,251

dimerisation, 176 isolation, 175 mass spec., 176 structure, 175

Biosynthetic pathways, 48 Biphenylene, 176 Bipolar non-protic solvents, 81,98,173,

252 Biradicals, 315,331, 337

oxygen, 315,330 stable, 338

Bisulphite addition comps., 207, 213 Bond

angles, 4 energy, 9,304 heterolytic fission, 20,299 homolytic fission, 20, 299

Bond-breaking AH+ and, 38

Bond lengths, 7 hybridisation and, 7

Bonding orbitals, 6 Branching, 321 Bredt's rule, 259 Bridged species, 105,118,129,335,377 Bromodealkylation, 162 Bromonium ions, cyclic, 180

detection, 181 isolation, 181

l-Bromotriptycene, 87 Brensted

acids, 53 bases, 53

Butyl rubber, 189

Cadmium Alkyls, 238 Cannizzaro reaction, 47,216

intramolecular, 217 isotopic labels in, 47,217 crossed, 216

Canonical structures, 19, 152 Carbamic acids, 122 Carbanions, 21,270-298

acetylide anion, 223,272,289,294 acidity and, 272,277 addition to C+C, 200 addition to C=O, 221-236,284 alkylation of, 288 as nucleophiles, 288 configuration, 276 cyclooctatetraenyl dianion, 275

Index 401

cyclopentadienyl anion, 275 deuterium exchange, 288 displacement reactions, 287 ElcB elimination and, 248,285 electronic effects in, 272 enolate anions, 279,290,295 formation, 271 in carbonation, 284 in Danens reaction, 290 in decarboxylation, 285 in Favorskii reaction, 294 in halogenation of ketones, 295 in Kolbe-Schmidt reaction, 291 in Michael reaction, 200 in Reimer-Tiemann reaction, 290 intermediates, 41,200,229,295 in Wurtz reaction, 289 oxidation, 294,307 rearrangement, 292 solvation, 45 stabilisation, 251,257,262,273,2% steric effects in, 276 tautomerism and, 277 trapping of, 286 triphenylmethyl, 271,272

Carbenes, 21 dichlorocarbene, 4,50, 267,290 intermediates, 119,266

Carbinolamine intermediates, 50,219 Carbocations, 21, 101-119

acyl, 102, 144,242,379 addition to 113, 188,225 allylic, 85, 105, 1% benzylic, 84,91, 102, 105, 112,371 bridged, 105,118,129,377 cycloheptatrienyl, 18, 104, 106 cyclohexadienyl, 159 cyclopropenyl, 18, 106 decomposition, 102 ethyl, 83, 104,380 formation, 101, 107, 120 hydride shifts in, 108, 109 in E l pathway, 248,261 in Friedel-Crafts, 108, 141, 145 in S,1 pathway, 78, 81, 83,90,371 loss of H@, 107, 111 methyl, 83, 104,380 2-methylpropyl, 78,83, 102, 104 n.m.r. and, 102, 181,393 phenonium, l05 phenyl, l69 propyl, 83,104,107,109 rearrangement, 32,102,107,109-119 reduction, 306 solvation, 45

400 Index

Ambident nucleophiles, 97 Amides

from Beckmann, 123 Hofmann reaction, 49, 122 hydrolysis, 239,245, 388 reduction, 214

Amidines basicity, 69 formation, 244

Aminoazo comps, 148 Anionic polymerisation, 200,226 Antarafacial shifts, 353 Anthracene, 17

photodimer, 337 transannular peroxide, 331

Anti-bonding orbitals, 6, 292 Anti-knock agents, 305 Anti-Markownikov addition, 317 Anti-oxidants, 330 Antiperiplanar conformation, 118,253 Arenium ions, 131 Arenonium ions, 131 Arndt-Eistert reaction, 119 Aromaticity, l4

cycloheptatrienyl cation, 18, 104, 106 cyclopentadienyl anion, 18, 275 cyclopropenyl cation, 18, 106 n.m.r. spectrum and, 18 requirements for, 17

Aromatic substitution, 41 electrophilic, 130-167 internal, 334, 381 nucleophilic, 167-177 radical, 331-335

Arrhenius equation, 38 Arrows

curved, l9 double-headed, 19

Arylation, 332 Aryne intermediates, 21, 174 Associative process, 239, 241 Atactic polymers, 322 Atomic orbitals, 1, 342 Aufbau principle, 3 Autoxidation, 306, 318,328

alkenes, 329 benzaldehyde, 306,330 cumene, l28 ethers, 329 tetralin, 329

Axial overlap, 6 h ides , 123, 194 Azoalkanes

photolysis, 304 thermolysis, 305

BAc2 pathway, 239,384 Baeyer-Villiger oxidation, 127 Barton reaction, 337 Base catalysis

general, 75 ion exchange resins, 226 specific, 75

Basicity aromaticity and, 69,72 Brensted and, 53 cation stability and, 67, 68, 72, 73 constant, 65 effect of solvent on, 66,67 H-bonding in, 67 inductive effect and, 22,66 Lewis and, 54 multiply bonded N and, 72 nucleophilicity and, 96 origin in organic comps., 66 ortho effects in, 71 softness, 96 steric effects in, 70,71

Basic strength aliphatic amines, 66 amides, 68 amidines, 69 aromatic bases, 69 catalysis and, 75 conjugate acids, 65 AP and, 66 guanidine, 68 heterocyclic bases, 72, 166 t e t r a a k y h m m ~ ~ ~ m hydroxides, 67

Beckmann rearrangement, 123 acid catalysis, 124 ~,'80 in, 125 intramolecularity, 126 solvent polarity and, 126 stereoselectivity, 124

Benzene aromaticity and, 14 bond lengths, 15 charge cloud, 15, 130 delocalisation in, 14, 130 heat of hydrogenation, 16 KekulC structures, 14, 194 m.0.s of, 14 n.m.r. signal, 18 ozonolysis, 194 planarity, 14 stability, 15

Benzilic acid rearrangement, 232 Benzoin condensation, 231

cyanide ion in, 231 thiazolium ylids in, 232

Benzotriazoles, 148, 176 Benzyne, 175,251

dimerisation, 176 isolation, 175 mass spec., 176 structure, 175

Biosynthetic pathways, 48 Biphenylene, 176 Bipolar non-protic solvents, 81,98,173,

252 Biradicals, 315,331, 337

oxygen, 315,330 stable, 338

Bisulphite addition comps., 207, 213 Bond

angles, 4 energy, 9,304 heterolytic fission, 20,299 homolytic fission, 20, 299

Bond-breaking AH+ and, 38

Bond lengths, 7 hybridisation and, 7

Bonding orbitals, 6 Branching, 321 Bredt's rule, 259 Bridged species, 105,118,129,335,377 Bromodealkylation, 162 Bromonium ions, cyclic, 180

detection, 181 isolation, 181

l-Bromotriptycene, 87 Brensted

acids, 53 bases, 53

Butyl rubber, 189

Cadmium Alkyls, 238 Cannizzaro reaction, 47,216

intramolecular, 217 isotopic labels in, 47,217 crossed, 216

Canonical structures, 19, 152 Carbamic acids, 122 Carbanions, 21,270-298

acetylide anion, 223,272,289,294 acidity and, 272,277 addition to C+C, 200 addition to C=O, 221-236,284 alkylation of, 288 as nucleophiles, 288 configuration, 276 cyclooctatetraenyl dianion, 275

Index 401

cyclopentadienyl anion, 275 deuterium exchange, 288 displacement reactions, 287 ElcB elimination and, 248,285 electronic effects in, 272 enolate anions, 279,290,295 formation, 271 in carbonation, 284 in Danens reaction, 290 in decarboxylation, 285 in Favorskii reaction, 294 in halogenation of ketones, 295 in Kolbe-Schmidt reaction, 291 in Michael reaction, 200 in Reimer-Tiemann reaction, 290 intermediates, 41,200,229,295 in Wurtz reaction, 289 oxidation, 294,307 rearrangement, 292 solvation, 45 stabilisation, 251,257,262,273,2% steric effects in, 276 tautomerism and, 277 trapping of, 286 triphenylmethyl, 271,272

Carbenes, 21 dichlorocarbene, 4,50, 267,290 intermediates, 119,266

Carbinolamine intermediates, 50,219 Carbocations, 21, 101-119

acyl, 102, 144,242,379 addition to 113, 188,225 allylic, 85, 105, 1% benzylic, 84,91, 102, 105, 112,371 bridged, 105,118,129,377 cycloheptatrienyl, 18, 104, 106 cyclohexadienyl, 159 cyclopropenyl, 18, 106 decomposition, 102 ethyl, 83, 104,380 formation, 101, 107, 120 hydride shifts in, 108, 109 in E l pathway, 248,261 in Friedel-Crafts, 108, 141, 145 in S,1 pathway, 78, 81, 83,90,371 loss of H@, 107, 111 methyl, 83, 104,380 2-methylpropyl, 78,83, 102, 104 n.m.r. and, 102, 181,393 phenonium, l05 phenyl, l69 propyl, 83,104,107,109 rearrangement, 32,102,107,109-119 reduction, 306 solvation, 45

402 Index

Carbocations (contd.) Chugaev reaction, 268 stabilisation, 21,84, 87, 104, 109,371, Cisoid conformation, 197,344, 350

382 stereochemistry of, 79, 84, 86, 104 structure, 104 triphenylmethyl, 84,87, 102, 103, 381 tropylium, 104

Carbon acids, 270 Carbonation, 284 Carbon, electron-deficient migration to,

108 Carbonyl group, 203-244

bond length, 11 characterisation, 219 conjugated, 12,23,200,205,223 dipole, 23,203 hydrates, 207 hydrogen bonding, 204,209 i.r. spectrum, 219 nucleophilic addition, 31, 200, 203-

244 protection, 210,211 protonation, 103,204 reactivity, 205 reduction, 212,214-219 structure, 23,203

Carboxylic derivs., reactions, 236244 acid hydrolysis, 240 base hydrolysis, 238 electronic effects in, 237 Grignard reagents, 238 leaving groups and, 237 reduction, 215 steric effects in, 238 tetrahedral intermediates in, 236

Catalysts acid, 42, 74 base, 75 cyanide ion, 231 heterogeneous, 143, 191,264 Lewis acid, 131, 189 metal, 191 nucleophilic, 99 reaction pathway and, 41 thiazolium ylids, 232

Cationic polymerisation, 189 Cellulose oxidation, 37 Chain length, 314, 324 Chain reactions, 300, 314 Chain transfer agents, 321 Chair conformation, 355 Charge transfer complexes, 131 Chelation, 291 Chirality, 87, 116,235,254, 278, 326 Chloral hydrate, 208 Chromatography, 43, 258

Claisen ester condensation, 229 Claisen rearrangement, 355 Claisen-Schmidt reaction, 226 Clemmensen reduction, 146 Colour

conjugation and, 13,331, 391 Combustion, heat of, 12 Competition experiments, 157 Complexes, dissociation, 27 Concerted reactions, 341

stereoselectivity in, 341 symmetry allowed, 348 symmetry forbidden, 348, 357

Configuration, 38, 88 apparent retention, 94 carbanions, 276 carbocations, 104 determination of relative, 88, 90 inversion, 87, 90, 190 oximes, 124 racemisation, 89, 90, 326 radicals, 309 retention, 93, 326

Conformation antiperiplanar, 118,253 chair, 355 cisoid, 197, 344, 350 eclipsed, 7,254 staggered, 7,254 synperiplanar, 253,269 tram diaxial, 255 transoid, 197, 350

Conjugate acids, 53, 65 bases, 53

Conjugate addition, 201 Conjugated carbonyl cornps., 12, 23,

200, 223 Conjugated dienes, 11 Conjugation, 11, 368 Conrotation, 345 Coordination polymerisation, 322 Copolymerisation, 322 Cope reaction, 268 Cope rearrangement, 354 Cracking, 112, 305 Cram's rule, 235 Cross-linking, 323 Crossover experiments, 116, 122, 126 Crowding, 8,110,162,165,183,206,235,

259, 261, 301, 311 Cumene, phenol from, 128 Curtius rearrangement, 122 Curved arrows, 19

Cyanides, addition to, 244 Cyanoethylation, 199 Cyanohydrins, 212 Cyclic bromonium ions, 180 Cycloadditions, 341, 348-352

2ne + 2ze, 348 4ne + 2ne, 348,349 symmetry allowed, 349 symmetry forbidden, 348

Cycloheptatrienyl cation, 18, 104, 106 Cyclohexadienyl cation, 159 Cyclohexadienyl radical, 331 Cyclooctatetraene, 16

dianion, 275 n.m.r. signal, 18 shape, l7

Cyclopentadiene acidity, 275 in Diels-Alder, 197, 350 tricyclic dimer, 351

Cyclopentadienyl anion, 18,275 Cyclopropanes

from carbenes, 50,266 thermolysis, 337

Cyclopropanone hydration, 209 intermediates, 294

Cyclopropenyl cation, 18, 106

Danens reaction, 290 Dealkylation, 143 Debromination, 264 Decarbonylation, 145, 335 Decarboxylation, 271,285

carbanions in, 271,285 cyclic T.S.s in, 286 electronic effects on, 286 trapping in, 286

Dehydration acid-catalysed, 103,220,225,247, 380 base-catalysed, 225,262

Delocalisation, 13 amidines, 69 benzene, 14,130 canonical structures and, 19 carbanions, 21,23,229,274 carbocations, 21, 83, 84, 87, 104, 110 carbonyl amps . , 23,205 carboxylate anions, 19,55,57 conditions necessary for, 18 dienes, 13, 194 energy, 13, 16 guanidine, 68 hyperconjugation and, 25

Index 403

in a complexes, 132, 151, 164 steric inhibition of, 26, 71, 172 tropylium cation, 18, 104, 106

6 steric parameter, 386 AG, 34 AG+, 38, 152, 158, 342, 394 AGe, 36,58,66,394 AH, 16,34

bond energy and, 35 AH+, 38,239,241,342,394 h p , 58,66, 394

Desulphurisation, 212 Deuterium

exchange, 131,158,174,211,288 kinetic isotope effect, 46, 136,139,288

Diamagnetism, 308 Diaryls, synthesis, 333 Diazoamino cornps., 147

rearrangement, 148 Diazo coupling, 26,28, 146

amines, 26, 147 electron density in, 148 intramolecular, 148 kinetics, 147, 148 pH and, 146 phenols, 147, 155 steric effects in, 27

Diazoketones, rearrangement, 119 Diazonium cations, 27, 119, 146

akyl, 107, 120 aryl, 121, 146 coupling by, 27, 146 decomposition, 104, 107, 120, 333 stability of, 120, 146 nucleophilic substitution, 169, 306

Diazotate anions, 146 Diazotisation

aliphatic amines, 107, 119 aromatic amines, 121, 146

Dichlorocarbenes, 4,50,267,290 Dieckmann reaction, 230 Diels-Alder reaction, 175, 197, 340, 349

cyclopentadiene in, 197 electronic effects in. 198, 349 endo v.exo addition, 350 4ne + 2ne, 349 reversibility, 351 secondary orbital interaction, 350 stereoselectivity in, 198, 349 steric effects in, 198,350 symmetry control in, 348 trapping in, 175 zwitterion intermediate, 351

402 Index

Carbocations (contd.) Chugaev reaction, 268 stabilisation, 21,84, 87, 104, 109,371, Cisoid conformation, 197,344, 350

382 stereochemistry of, 79, 84, 86, 104 structure, 104 triphenylmethyl, 84,87, 102, 103, 381 tropylium, 104

Carbon acids, 270 Carbonation, 284 Carbon, electron-deficient migration to,

108 Carbonyl group, 203-244

bond length, 11 characterisation, 219 conjugated, 12,23,200,205,223 dipole, 23,203 hydrates, 207 hydrogen bonding, 204,209 i.r. spectrum, 219 nucleophilic addition, 31, 200, 203-

244 protection, 210,211 protonation, 103,204 reactivity, 205 reduction, 212,214-219 structure, 23,203

Carboxylic derivs., reactions, 236244 acid hydrolysis, 240 base hydrolysis, 238 electronic effects in, 237 Grignard reagents, 238 leaving groups and, 237 reduction, 215 steric effects in, 238 tetrahedral intermediates in, 236

Catalysts acid, 42, 74 base, 75 cyanide ion, 231 heterogeneous, 143, 191,264 Lewis acid, 131, 189 metal, 191 nucleophilic, 99 reaction pathway and, 41 thiazolium ylids, 232

Cationic polymerisation, 189 Cellulose oxidation, 37 Chain length, 314, 324 Chain reactions, 300, 314 Chain transfer agents, 321 Chair conformation, 355 Charge transfer complexes, 131 Chelation, 291 Chirality, 87, 116,235,254, 278, 326 Chloral hydrate, 208 Chromatography, 43, 258

Claisen ester condensation, 229 Claisen rearrangement, 355 Claisen-Schmidt reaction, 226 Clemmensen reduction, 146 Colour

conjugation and, 13,331, 391 Combustion, heat of, 12 Competition experiments, 157 Complexes, dissociation, 27 Concerted reactions, 341

stereoselectivity in, 341 symmetry allowed, 348 symmetry forbidden, 348, 357

Configuration, 38, 88 apparent retention, 94 carbanions, 276 carbocations, 104 determination of relative, 88, 90 inversion, 87, 90, 190 oximes, 124 racemisation, 89, 90, 326 radicals, 309 retention, 93, 326

Conformation antiperiplanar, 118,253 chair, 355 cisoid, 197, 344, 350 eclipsed, 7,254 staggered, 7,254 synperiplanar, 253,269 tram diaxial, 255 transoid, 197, 350

Conjugate acids, 53, 65 bases, 53

Conjugate addition, 201 Conjugated carbonyl cornps., 12, 23,

200, 223 Conjugated dienes, 11 Conjugation, 11, 368 Conrotation, 345 Coordination polymerisation, 322 Copolymerisation, 322 Cope reaction, 268 Cope rearrangement, 354 Cracking, 112, 305 Cram's rule, 235 Cross-linking, 323 Crossover experiments, 116, 122, 126 Crowding, 8,110,162,165,183,206,235,

259, 261, 301, 311 Cumene, phenol from, 128 Curtius rearrangement, 122 Curved arrows, 19

Cyanides, addition to, 244 Cyanoethylation, 199 Cyanohydrins, 212 Cyclic bromonium ions, 180 Cycloadditions, 341, 348-352

2ne + 2ze, 348 4ne + 2ne, 348,349 symmetry allowed, 349 symmetry forbidden, 348

Cycloheptatrienyl cation, 18, 104, 106 Cyclohexadienyl cation, 159 Cyclohexadienyl radical, 331 Cyclooctatetraene, 16

dianion, 275 n.m.r. signal, 18 shape, l7

Cyclopentadiene acidity, 275 in Diels-Alder, 197, 350 tricyclic dimer, 351

Cyclopentadienyl anion, 18,275 Cyclopropanes

from carbenes, 50,266 thermolysis, 337

Cyclopropanone hydration, 209 intermediates, 294

Cyclopropenyl cation, 18, 106

Danens reaction, 290 Dealkylation, 143 Debromination, 264 Decarbonylation, 145, 335 Decarboxylation, 271,285

carbanions in, 271,285 cyclic T.S.s in, 286 electronic effects on, 286 trapping in, 286

Dehydration acid-catalysed, 103,220,225,247, 380 base-catalysed, 225,262

Delocalisation, 13 amidines, 69 benzene, 14,130 canonical structures and, 19 carbanions, 21,23,229,274 carbocations, 21, 83, 84, 87, 104, 110 carbonyl amps . , 23,205 carboxylate anions, 19,55,57 conditions necessary for, 18 dienes, 13, 194 energy, 13, 16 guanidine, 68 hyperconjugation and, 25

Index 403

in a complexes, 132, 151, 164 steric inhibition of, 26, 71, 172 tropylium cation, 18, 104, 106

6 steric parameter, 386 AG, 34 AG+, 38, 152, 158, 342, 394 AGe, 36,58,66,394 AH, 16,34

bond energy and, 35 AH+, 38,239,241,342,394 h p , 58,66, 394

Desulphurisation, 212 Deuterium

exchange, 131,158,174,211,288 kinetic isotope effect, 46, 136,139,288

Diamagnetism, 308 Diaryls, synthesis, 333 Diazoamino cornps., 147

rearrangement, 148 Diazo coupling, 26,28, 146

amines, 26, 147 electron density in, 148 intramolecular, 148 kinetics, 147, 148 pH and, 146 phenols, 147, 155 steric effects in, 27

Diazoketones, rearrangement, 119 Diazonium cations, 27, 119, 146

akyl, 107, 120 aryl, 121, 146 coupling by, 27, 146 decomposition, 104, 107, 120, 333 stability of, 120, 146 nucleophilic substitution, 169, 306

Diazotate anions, 146 Diazotisation

aliphatic amines, 107, 119 aromatic amines, 121, 146

Dichlorocarbenes, 4,50,267,290 Dieckmann reaction, 230 Diels-Alder reaction, 175, 197, 340, 349

cyclopentadiene in, 197 electronic effects in. 198, 349 endo v.exo addition, 350 4ne + 2ne, 349 reversibility, 351 secondary orbital interaction, 350 stereoselectivity in, 198, 349 steric effects in, 198,350 symmetry control in, 348 trapping in, 175 zwitterion intermediate, 351

404 Index

Dienes, 11 addition to, 194-198 cisoid conformation, 197,350 conjugated, 11 Cope rearrangement, 354 cyclisation, 346 cycloaddition to, 348 Diels-Alder reaction, 197,349 excited state, 13 heat of hydrogenation, 16,194 isolated, 11 m.0.s of, 12 polymerisation, 323

Dienone intermediates, 356 Dienonelphenol rearrangement, 115 Dienophiles, 198,350 Digonal hybridisation, 5 Dimedone, 202 Dimroth's E, parameter, 391

solvatochromic shifts, 391 solvent polarity, 391 Y and, 392

Dinitrofluorobenzene proteins and, 172

1,2-Diols formation, 189 rearrangement, 113

1,l-Diphenyl-2-picrylhydrazyl, 301 Diphenylpolyenes, 13 1,3-Dipolar addition, 192, 194,351 Dipole moments, 22, 156, 165,203 Diradicals, 315, 330, 337

stable, 338 Displacement, 30 Disproportionation, 216,305,321 Disrotation, 345 Dissociative process, 241

E,, 38 Ecli~sed conformation. 7.254 , -

~ l e ~ t r o c ~ c l i c reactions, 341, 344-348 Electrolytic oxidation, 307 Electrolytic reduction, 3CV Electromeric effect, 24 Electron configuration, 3 Electron density, 21,26, 29,393 Electron-donating groups, 23,26

addition to and, 183 addition to C=O and, 205,206 aromatic substitution and, 153, 158 pinacol change and, 115

Electronegativity, 21,22,95 Electrons, lone pair, 10, 72 Electron spin, paired, 2, 308 Electron-withdrawing groups, 23

acidity and, 59,61,62,272

addition to C===C and, 183 addition to C=O and, 205,226 aromatic substitution and, 151, 158 basicity and, 67,70 elimination and, 251, 262

Electrophiles, 29 Electrophilic addition to C+C, 31, 178-

194 bromine, 51, 179 carbocations, 113, 180, 184, 187, 188,

225 cationic polymerisation, 189 cyclic bromonium ions, 180 1,3-dipolar, 192, 194, 351 effect of added nucleophiles, 179 hydration, 187 hydroboration, 187 hydrogenation, 191 hydrogen bromide, 184,201 hydroxylation, 189 inductive effect in, 185 Lewis acids, 181 mesomeric effect in, 182 orientation, 184 ozone, 192 peroxy acids, 190 n complexes in, 180, 184 proton, 103, 184, 187 rate, 183, 185 rearrangements in, 185, 187 solvent and, 182 stereoselectivity, 51, 180, 182, 186,

188,189, 191 steric effects, 181 vinyl halides, 185

Electrophilic addition to C=Ca, 194

Electrophilic substitution, aromatic, 31, 130-167,381

1 ,2-v. l ,4-addition, 195 as additionlelimination, 133 complexing with substituent, 160 deuterium exchange, 131, 158 electronic effects in, 148, 158, 159 energetics of, 132, 136 field effect in, 152 hyperconjugation in, 153 inductive effect in, 22, 152, 153, 156,

160 intermediates, isolation, 136, 142 internal, 381 ipso, 161 isotope effects, 46, 139 kinetic control, 151, 163, 164 Lewis acids in, 131, 138, 141,144, 163 mesomeric effect in, 154, 155, 164

o-/p-ratios, 159 n complexes in, 131 partial rate factors, 156 selectivity in, 158 a complexes in, 41, 131,151,159 solvent and, 161 steric effects in, 153, 158, 159, 162,

165 substituent effects, 150-163 thermodynamic control, 163, 164 transition states, 135, 151, 158

1,3-Elimination, 293 E l elimination, 248,381

alkene stability and, 249,256 carbocations and, 247,248 orientation in, 249 Saytzev mode, 249 SN1 and, 248,260 steric effects in, 261 structure and, 249 v. E2,249,252

ElcB elimination, 249 activation energy, 250 carbanions and, 248,249,257 electron-withdrawal and, 251 in aldol dehydration, 225,251 in benzyne formation, 251 isotopic exchange and, 250 leaving group and, 251 structure and, 251

E2 elimination, 251-260 alkene stability and, 253,256 base strength and, 252 bond strength and, 252 conformation and, 253,255 electronic effects in, 257 Hofmann mode, 256 in cyclic comps., 255 kinetic isotope effect, 252 leaving group and, 252,257 orientation in, 256 Saytzev mode, 256 SN2 and, 252,254,260 solvent and, 252,255 stereoselectivity in, 253,264 steric effects in, 258 strength of base and, 257 variable T.S. in, 256

E,(1 ,l-)elimination, 266 bases and, 266 carbenes in, 50,266 isotopic labelling in, 266

Ei elimination, pyrolytic, 268, 340 Cope reaction, 268 stereoselectivity, 268,269

Elimination v. substitution, 100, 260

Index 405

alkene stability and, 261 base size and, 261 basicitylnucleophilicity in, 262 change of pathway, 260 E1/SN1 ratio, 260 E2/SN2 ratio, 260 entropy and, 262 leaving group and, 261 solvent and, 260 steric effects in, 261,262 structure and, 260,261 temperature and, 262

Enamines, 221 End group analysis, 172 Endo addition, 350 Energetics of reaction, 33 Energy barriers, 37 Energy profiles, 37 Enolate anions, 279, 290,295 Enolisation, 201,219,225,280,297,356 Enthalpy, 34

of activation, 38 Entropy, 34

cyclisation and, 36 energy partition and, 35 hydrogen bonding and, 36 of activation, 39,79 rotational, 36 temperature and, 36 translational, 36, 58, 239

Epoxides, as intermediates, 94, 190 hydrolysis, 190

Epoxyesters, U$-, 290 E; 373 Eauilibrium

acidity and, 54 basicity and, 65 constant, K, 35 control, 43, 163, 165, 171, 195 entropy and, 36 free energy and, 35

E.s.r. spectroscopy, 308 spin trapping in, 309 splitting in, 308

E, steric parameter, 386 Ester hydrolysis

acid-catalysed, 240 acyl-oxygen fission, 47,239 alkyl-oxygen fission, 47,241 BAC2 pathway, 239,384 base-catalysed, 239,366, 367,374 isotopic labels in, 47, 89, 238 steric effects in, 241,361,385

Esterification AAC1 pathway, 242,379

404 Index

Dienes, 11 addition to, 194-198 cisoid conformation, 197,350 conjugated, 11 Cope rearrangement, 354 cyclisation, 346 cycloaddition to, 348 Diels-Alder reaction, 197,349 excited state, 13 heat of hydrogenation, 16,194 isolated, 11 m.0.s of, 12 polymerisation, 323

Dienone intermediates, 356 Dienonelphenol rearrangement, 115 Dienophiles, 198,350 Digonal hybridisation, 5 Dimedone, 202 Dimroth's E, parameter, 391

solvatochromic shifts, 391 solvent polarity, 391 Y and, 392

Dinitrofluorobenzene proteins and, 172

1,2-Diols formation, 189 rearrangement, 113

1,l-Diphenyl-2-picrylhydrazyl, 301 Diphenylpolyenes, 13 1,3-Dipolar addition, 192, 194,351 Dipole moments, 22, 156, 165,203 Diradicals, 315, 330, 337

stable, 338 Displacement, 30 Disproportionation, 216,305,321 Disrotation, 345 Dissociative process, 241

E,, 38 Ecli~sed conformation. 7.254 , -

~ l e ~ t r o c ~ c l i c reactions, 341, 344-348 Electrolytic oxidation, 307 Electrolytic reduction, 3CV Electromeric effect, 24 Electron configuration, 3 Electron density, 21,26, 29,393 Electron-donating groups, 23,26

addition to and, 183 addition to C=O and, 205,206 aromatic substitution and, 153, 158 pinacol change and, 115

Electronegativity, 21,22,95 Electrons, lone pair, 10, 72 Electron spin, paired, 2, 308 Electron-withdrawing groups, 23

acidity and, 59,61,62,272

addition to C===C and, 183 addition to C=O and, 205,226 aromatic substitution and, 151, 158 basicity and, 67,70 elimination and, 251, 262

Electrophiles, 29 Electrophilic addition to C+C, 31, 178-

194 bromine, 51, 179 carbocations, 113, 180, 184, 187, 188,

225 cationic polymerisation, 189 cyclic bromonium ions, 180 1,3-dipolar, 192, 194, 351 effect of added nucleophiles, 179 hydration, 187 hydroboration, 187 hydrogenation, 191 hydrogen bromide, 184,201 hydroxylation, 189 inductive effect in, 185 Lewis acids, 181 mesomeric effect in, 182 orientation, 184 ozone, 192 peroxy acids, 190 n complexes in, 180, 184 proton, 103, 184, 187 rate, 183, 185 rearrangements in, 185, 187 solvent and, 182 stereoselectivity, 51, 180, 182, 186,

188,189, 191 steric effects, 181 vinyl halides, 185

Electrophilic addition to C=Ca, 194

Electrophilic substitution, aromatic, 31, 130-167,381

1 ,2-v. l ,4-addition, 195 as additionlelimination, 133 complexing with substituent, 160 deuterium exchange, 131, 158 electronic effects in, 148, 158, 159 energetics of, 132, 136 field effect in, 152 hyperconjugation in, 153 inductive effect in, 22, 152, 153, 156,

160 intermediates, isolation, 136, 142 internal, 381 ipso, 161 isotope effects, 46, 139 kinetic control, 151, 163, 164 Lewis acids in, 131, 138, 141,144, 163 mesomeric effect in, 154, 155, 164

o-/p-ratios, 159 n complexes in, 131 partial rate factors, 156 selectivity in, 158 a complexes in, 41, 131,151,159 solvent and, 161 steric effects in, 153, 158, 159, 162,

165 substituent effects, 150-163 thermodynamic control, 163, 164 transition states, 135, 151, 158

1,3-Elimination, 293 E l elimination, 248,381

alkene stability and, 249,256 carbocations and, 247,248 orientation in, 249 Saytzev mode, 249 SN1 and, 248,260 steric effects in, 261 structure and, 249 v. E2,249,252

ElcB elimination, 249 activation energy, 250 carbanions and, 248,249,257 electron-withdrawal and, 251 in aldol dehydration, 225,251 in benzyne formation, 251 isotopic exchange and, 250 leaving group and, 251 structure and, 251

E2 elimination, 251-260 alkene stability and, 253,256 base strength and, 252 bond strength and, 252 conformation and, 253,255 electronic effects in, 257 Hofmann mode, 256 in cyclic comps., 255 kinetic isotope effect, 252 leaving group and, 252,257 orientation in, 256 Saytzev mode, 256 SN2 and, 252,254,260 solvent and, 252,255 stereoselectivity in, 253,264 steric effects in, 258 strength of base and, 257 variable T.S. in, 256

E,(1 ,l-)elimination, 266 bases and, 266 carbenes in, 50,266 isotopic labelling in, 266

Ei elimination, pyrolytic, 268, 340 Cope reaction, 268 stereoselectivity, 268,269

Elimination v. substitution, 100, 260

Index 405

alkene stability and, 261 base size and, 261 basicitylnucleophilicity in, 262 change of pathway, 260 E1/SN1 ratio, 260 E2/SN2 ratio, 260 entropy and, 262 leaving group and, 261 solvent and, 260 steric effects in, 261,262 structure and, 260,261 temperature and, 262

Enamines, 221 End group analysis, 172 Endo addition, 350 Energetics of reaction, 33 Energy barriers, 37 Energy profiles, 37 Enolate anions, 279, 290,295 Enolisation, 201,219,225,280,297,356 Enthalpy, 34

of activation, 38 Entropy, 34

cyclisation and, 36 energy partition and, 35 hydrogen bonding and, 36 of activation, 39,79 rotational, 36 temperature and, 36 translational, 36, 58, 239

Epoxides, as intermediates, 94, 190 hydrolysis, 190

Epoxyesters, U$-, 290 E; 373 Eauilibrium

acidity and, 54 basicity and, 65 constant, K, 35 control, 43, 163, 165, 171, 195 entropy and, 36 free energy and, 35

E.s.r. spectroscopy, 308 spin trapping in, 309 splitting in, 308

E, steric parameter, 386 Ester hydrolysis

acid-catalysed, 240 acyl-oxygen fission, 47,239 alkyl-oxygen fission, 47,241 BAC2 pathway, 239,384 base-catalysed, 239,366, 367,374 isotopic labels in, 47, 89, 238 steric effects in, 241,361,385

Esterification AAC1 pathway, 242,379

406 Index

Esterification (contd.) AAc2 pathway, 241,384 AA,l pathway, 241,380 acid-catalysed, 240, 378 acyl-oxygen fission, 88,240,242 alkyl-oxygen fission, 240 isotope labels in, 88,241 steric effects in, 242

Esters acyloin condensation, 218 Claisen condensation, 229 hydrolysis, 238-244,365,367,378,

384 reduction, 215

E, solvent parameter, 391 Ethanoate anion, 19 Excited state

carbon, 4 dienes, 13

Exclusion principle, 2 Exo addition, 350 Exocyclic methylenes, 234

Fats, rancidity, 328 Favorskii rearrangement, 294 Fenton's reagent, 306 Ferrocene, 275 Field effects, 22, 152, 364 Flash photolysis, 304 Fluorination, 121, 140, 170,315,326 Free energy, Gibbs, 34

change and K, 35,359 of activation, 38, 359 standard, 35

Freezing point depression benzoic acid, 242 ketones, 103 mesitoic acid, 243 nitric acid, 134

Friedel-Crafts reaction acylation, 143 acylium ions in, 144 alkylation, 141 carbocations in, 108, 141, 145 dealkylation in, 143 formylation, 145 intermediates in, 141, 144 intramolecular, 243 Lewis acids in, 108, 141, 144 polarised complexes in, 108, 141,144 polyalkylation, 143 rearrangements in, 108, 142, 143, 163 solvent and, 143, 144 thermodynamic control in, 163 with alcohols, 142 with alkenes, 142

with cyclic anhydrides, 146 Frontier orbital approach, 344 f,, 156, 159,333

Gatterman-Koch reaction, 145 Gegen ions, 91 General acid catalysis, 74,208,209,220,

297 General base catalysis, 75, 208 Gibbs free energy, G, 34 1,2-Glycols

ck , 189 rearrangement, l l3 tram, 190

Gomberg reaction, 333 Grignard reagents

addition to 6 C + 0 , 201 addition to C%N, 244 addition to 6 0 , 2 2 1 , 2 3 5 , 2 3 8 structure, 221

Ground state carbon, 3 dienes, 13 halogenobenzenes, 156

Grunwald-Winstein equation, 389 compound parameter, m, in, 390 derivation of, 389 diagnostic use of, 391 limitations of, 391 solvent parameter, Y, in, 389 standard reaction for, 389 standard solvent for, 389

Gutta percha, 323

Half-life, 301 Haloform reaction, 237, 296 Halogenation

alkanes, 300, 323 alkenes, 179,186,313 benzene, 138,316 ketones, 295

Hammett equation, 362 additional parameters, 374, 388, 395 derivation of, 362 deviations from, 375 empirical nature of, 395 implications of, 394 reaction pathway, and, 375 solvent effects and, 388 spectroscopic correlations, 392 standard reaction for, 362,395 steric effects and, 361,383 thermodynamic implications of, 394

Hammett plots, 359 change in rate-limiting step and, 383 change in reaction pathway and, 378

downward deviations in, 380 solvent effects and, 388 steric effects and, 361,383 upward deviations in, 375 uses of, 374

Hammond's principle, 137 Hard bases, 96 Heat of combustion, 12 Heat of hydration, 97 Heat of hydrogenation, 12,16

benzene, l6 cyclohexene, l 6 cyclooctatetraene, 16 cyclooctene, 16 dienes, 16, 194

Heat of reaction, 34 Heisenberg principle, 2 Hemi-acetals, 209 Heterolysis, 20, 129, 178,299 Hexacene, 331 Hofmann

elimination, 256 reaction of amides, 49, 122

HOMO, 344 Homolysis, 20,129, 179,299 Hybridisation, 4 Hydration

C=C, 42,187 C==O. 207 heat of, 97

Hydride transfer, 108,109,214,215,216 Hvdroboration, 187 ~ i d r o ~ e n abstiaction, 309,316,321 Hydrogenation

*C, 191 M, 191 C==O, 214 heat of, 16 homogeneous catalysis in, 192 stereoselectivity in, 191

Hydrogen bonding acidity and, 63,64 C==O and, 204,209,286 intermolecular, 36,282 intramolecular, 36,208,281 solvation and, 57,67,252,282

Hydrogen peroxide Fenton's reagent, 306 hydroxylation of *C, 189 oxidation of ketones, 127

Hydrogen shifts 1,3-photochemical, 354 1,s-thermal, 353 1,7-photochemical, 354 1,7-thermal, 354

Hydrolysis,

Index 407

esters, 238, 374 halides, 77

Hydroperoxides formation, 328 in autoxidation, 328 rearrangement, l28

Hydroxamic acids, Lossen degradation, 123

Hydroxylation, 189 Hyperconjugation, 25

alkene stability and, 26 aromatic substitution and, 153 carbocation stability and, 83

Hypochlorites, alkyl, 327 Hiickel's rule, 17, 106 Hund's rule, 3,275

Imino-ethers, 245 Inductive effect, 21

acidity and, 273 basicity and, 66 electronegativity and, 22 electrophilic substitution and, 152,

156,160 Inductomeric effect, 24 Insertion reactions, 50,266,267 Intermediates

bridged, 105,118,129,335,377 catalysts and, 42 criteria for, 49 cyclic, 180,189,227 isolation, 48, 136, 142, 171,290 models for T.S., 41, 51,78,137, 151 spectroswpic detection, 50, 144, 171,

181,219,237 study of, 49 tetrahedral, 236 trapping, 50, 175,286, 356 Wheland, 41,131,151

Intermolecular rearrangements, 143, 149,278

Intimate ion pairs, 91,249,291 Intramolecular rearrangements, 116,

122, 126, 127, 128,217,232,279, 355

Inversion in SN1, 90 in SN2, 88,89, 190

Iodoform, 297 Iodonium ions, cyclic, 186 Ionisation

AG* and, 58 solvent and, 56,102, 388 temperature and, 64

Ion pairs, 20,45,57,64,79,102,136, 141

406 Index

Esterification (contd.) AAc2 pathway, 241,384 AA,l pathway, 241,380 acid-catalysed, 240, 378 acyl-oxygen fission, 88,240,242 alkyl-oxygen fission, 240 isotope labels in, 88,241 steric effects in, 242

Esters acyloin condensation, 218 Claisen condensation, 229 hydrolysis, 238-244,365,367,378,

384 reduction, 215

E, solvent parameter, 391 Ethanoate anion, 19 Excited state

carbon, 4 dienes, 13

Exclusion principle, 2 Exo addition, 350 Exocyclic methylenes, 234

Fats, rancidity, 328 Favorskii rearrangement, 294 Fenton's reagent, 306 Ferrocene, 275 Field effects, 22, 152, 364 Flash photolysis, 304 Fluorination, 121, 140, 170,315,326 Free energy, Gibbs, 34

change and K, 35,359 of activation, 38, 359 standard, 35

Freezing point depression benzoic acid, 242 ketones, 103 mesitoic acid, 243 nitric acid, 134

Friedel-Crafts reaction acylation, 143 acylium ions in, 144 alkylation, 141 carbocations in, 108, 141, 145 dealkylation in, 143 formylation, 145 intermediates in, 141, 144 intramolecular, 243 Lewis acids in, 108, 141, 144 polarised complexes in, 108, 141,144 polyalkylation, 143 rearrangements in, 108, 142, 143, 163 solvent and, 143, 144 thermodynamic control in, 163 with alcohols, 142 with alkenes, 142

with cyclic anhydrides, 146 Frontier orbital approach, 344 f,, 156, 159,333

Gatterman-Koch reaction, 145 Gegen ions, 91 General acid catalysis, 74,208,209,220,

297 General base catalysis, 75, 208 Gibbs free energy, G, 34 1,2-Glycols

ck , 189 rearrangement, l l3 tram, 190

Gomberg reaction, 333 Grignard reagents

addition to 6 C + 0 , 201 addition to C%N, 244 addition to 6 0 , 2 2 1 , 2 3 5 , 2 3 8 structure, 221

Ground state carbon, 3 dienes, 13 halogenobenzenes, 156

Grunwald-Winstein equation, 389 compound parameter, m, in, 390 derivation of, 389 diagnostic use of, 391 limitations of, 391 solvent parameter, Y, in, 389 standard reaction for, 389 standard solvent for, 389

Gutta percha, 323

Half-life, 301 Haloform reaction, 237, 296 Halogenation

alkanes, 300, 323 alkenes, 179,186,313 benzene, 138,316 ketones, 295

Hammett equation, 362 additional parameters, 374, 388, 395 derivation of, 362 deviations from, 375 empirical nature of, 395 implications of, 394 reaction pathway, and, 375 solvent effects and, 388 spectroscopic correlations, 392 standard reaction for, 362,395 steric effects and, 361,383 thermodynamic implications of, 394

Hammett plots, 359 change in rate-limiting step and, 383 change in reaction pathway and, 378

downward deviations in, 380 solvent effects and, 388 steric effects and, 361,383 upward deviations in, 375 uses of, 374

Hammond's principle, 137 Hard bases, 96 Heat of combustion, 12 Heat of hydration, 97 Heat of hydrogenation, 12,16

benzene, l6 cyclohexene, l 6 cyclooctatetraene, 16 cyclooctene, 16 dienes, 16, 194

Heat of reaction, 34 Heisenberg principle, 2 Hemi-acetals, 209 Heterolysis, 20, 129, 178,299 Hexacene, 331 Hofmann

elimination, 256 reaction of amides, 49, 122

HOMO, 344 Homolysis, 20,129, 179,299 Hybridisation, 4 Hydration

C=C, 42,187 C==O. 207 heat of, 97

Hydride transfer, 108,109,214,215,216 Hvdroboration, 187 ~ i d r o ~ e n abstiaction, 309,316,321 Hydrogenation

*C, 191 M, 191 C==O, 214 heat of, 16 homogeneous catalysis in, 192 stereoselectivity in, 191

Hydrogen bonding acidity and, 63,64 C==O and, 204,209,286 intermolecular, 36,282 intramolecular, 36,208,281 solvation and, 57,67,252,282

Hydrogen peroxide Fenton's reagent, 306 hydroxylation of *C, 189 oxidation of ketones, 127

Hydrogen shifts 1,3-photochemical, 354 1,s-thermal, 353 1,7-photochemical, 354 1,7-thermal, 354

Hydrolysis,

Index 407

esters, 238, 374 halides, 77

Hydroperoxides formation, 328 in autoxidation, 328 rearrangement, l28

Hydroxamic acids, Lossen degradation, 123

Hydroxylation, 189 Hyperconjugation, 25

alkene stability and, 26 aromatic substitution and, 153 carbocation stability and, 83

Hypochlorites, alkyl, 327 Hiickel's rule, 17, 106 Hund's rule, 3,275

Imino-ethers, 245 Inductive effect, 21

acidity and, 273 basicity and, 66 electronegativity and, 22 electrophilic substitution and, 152,

156,160 Inductomeric effect, 24 Insertion reactions, 50,266,267 Intermediates

bridged, 105,118,129,335,377 catalysts and, 42 criteria for, 49 cyclic, 180,189,227 isolation, 48, 136, 142, 171,290 models for T.S., 41, 51,78,137, 151 spectroswpic detection, 50, 144, 171,

181,219,237 study of, 49 tetrahedral, 236 trapping, 50, 175,286, 356 Wheland, 41,131,151

Intermolecular rearrangements, 143, 149,278

Intimate ion pairs, 91,249,291 Intramolecular rearrangements, 116,

122, 126, 127, 128,217,232,279, 355

Inversion in SN1, 90 in SN2, 88,89, 190

Iodoform, 297 Iodonium ions, cyclic, 186 Ionisation

AG* and, 58 solvent and, 56,102, 388 temperature and, 64

Ion pairs, 20,45,57,64,79,102,136, 141

408 Index

Ion pairs (contd.) intimate, 91, 249, 291 solvation, 45, 57, 81, 390 solvent separated, 91

Ipso substitution, 161, 169 steric effects in, 162

Isocyanate intermediates, 49, 122 Isomer distribution, 158 Isomerisation, cis + tram, 315 Isoprene, 323 Isotope effects, kinetic, 46,83,139, 252,

288,295 Isotopic labels, 47

bromide, 141 carbon, 48, 108,233, 355 deuterium, 47, 117, 131, 174,216,

217,224,233,250,264,278,288 iodine, 89 monitoring, 48,89 nitrogen, 170 oxygen, 47,89,125, 127,189,207,239 scrambling of, 108,141,169 sulphur, 165

K, 35,359 k, 38, 359, 374 K,, 54, 65

AGe and, 58 K*, 65

AGe and, 66 Ketenes, 119 B-Keto-acids, decarboxylation, 286 Keto-enol tautomerism, 201,219,225

carbanions in, 278 catalysis of, 277 equilibrium and structure, 280,297 hydrogen bonding and, 281 mechanism of, 278 solvent and, 282

Ketones, halogenation, 295 bromination, 41,51, 76,297 electronic effects in, 2% enolisation in, 297 general acid catalysis, 297 general base catalysis, 76 orientation in, 2%, 297 rate of, 295,2%, 297

Ketoximes, Beckmann rearrangement, 123

Ketyls, 218 Kinetic acidity, 280 Kinetic control, 42, 151

addition to C=0, 235 addition to dienes, 195 Diels-Alder, 350

nitration, 43 protonation, 283

Kinetic data, interpretation, 40, 44, 78 Kinetic isotope effects, 46

carbon, 47 chlorine, 47 deuterium, 44,83,252,288,295 primary, 44,252,288,295 secondary, 83

Kinetics of reaction, 36 isotope effects in, 46 measurement of, 39,89 rate-limiting step in, 39

Knocking, 305 Knoevenagel reaction, 228 Kolbe electrolytic synthesis, 307 Kolbe-Schmidt reaction, 291

LaetPms, 126 Lactone intermediates, 94, 127, 228 Lateral overlap, orbitals, 9 Lead alkyls, 301

anti-knock, 305 thermolysis, 301, 304, 324

Leaving groups, 98,99, 127, 139,237 ability of, 98, 251 bromobenzene sulphonate ion, 375 cyanide ion, 232 ethanoate anion, 228 ethoxide ion, 229 hydride ion, l68 hydrogen bonding and, 252 hydroxyl ion, 225,253 in elimination, 247,251,253 internal, 100 nitrogen, 100,104,107,114, 121,123,

169,305 protonated, 103, 125 relative ability, 98, 251, 253 tosylate, 89,98,100,253 triflate, 98

Levelling effect, water, 55 Lewis acids, 29 Lewis bases, 29 Light absorption, colour and, 13 Lindlar catalyst, 191,223 Linear free energy relationships, 358-

395 Lithium

alkyls, 223, 238, 293 aryls, 223,233,293

Lithium aluminium hydride, 214 Localised orbitals, 6 Lone pairs, 10,72

in neighbouring groups, 94 protonated, 99,103

X Lossen rearrangement, 123 k 84

LUMO, 344

Magnetic moment, electronic, 308 Markownikov addition, 184 Mass spectrometry, 176 m, compound parameter, 390

diagnostic use of, 391 Mechanistic borderline, 91 Meerwein-Ponndorf reaction, 215 Meisenheimer complexes, 171 Mesomeric effect, 23, 154, 156, 172,238,

278 Meta (m)-directing groups, 150 Metal alkyls

carbonation, 284 thermolysis, 304 Wurtz reaction and, 289

Michael reaction, 200 Migration

origin, 116 terminus, 116 to electron-deficient C, 109, 110-119 to electron-deficient N, 122-126 to electron-deficient 0 , 127-129

Migratory aptitude, 114, 129 conformation of T.S. and, 118

Mixed SN1/SN2 pathway, 92 Models for T.S., 41,51,78,137,151,

194,254 Molecularity, 79 Molecular orbitals, 5,343 Molozonides, 193 Monomers, 321 Mustard gas, 96

Naphthalene, 17 nitration, 164 sulphonation, 164

N-brornosuccinimide, 327 Neighbouring group participation, 93-

96,181,377 Neopentyl rearrangements, 110 Newman projections, 7,235 Nitration, 31,45, 133-138

dilute HNO, in, 137 isotope effects in, 46 kinetics of, 134, 135 naphthalene, 164 nitronium Buoroborate in, 135 NO? in, 134

Nitrating mixture, 133 Nitrenes, 21, 122

carbonyl, l22 Nitriles, reactions, 244

Nitroalkanes acidity, 272, 280 addition to C=O, 226 tautomerism, 283

Nitrodealkylation, 162 Nitrodehalogenation, 162 Nitroeen, electron-deficient, migration

t;, l20 Nitroniurn ion, 45, 103,134 Nitrosating agents, 119 Nitrosation

phenol, 137 primary aliphatic amines, 107, 119 ~rimary aromatic amines, 120 secondary amines, 121 tertiary amines, 121

Nitrosoniurn ion, 120, 137 Nitro~otrialk~lammonium cation, 121 Nitrous acid, protonated, 120 N.m.r. spectroscopy, 18,48, 102, 106,

111, 126, 129, 159, 181,219 aromaticity and, 18 13c, 49,106, 111,393 carboxyl protonation and, 240 Grignard reagents and, 221 ozonolvsis and, 193, 194 ox and; 393 triphenylmethyl dimer, 44,301

N-nitroso comwunds, 121 Nodal

plane, 3,343 surface, 2

Nodes, 343 Non-bonded interaction, 7 Nucleophiles, 29

ambident, 97 Nucleophilic addition to =, 198

carbanions in, l99 cyanoethylation, 199 hydrogen cyanide, 199 methanol, 199 Michael reaction, 200

Nucleo~hilic addition to =m, 206

conjugate addition, 201 Grignard reagents, 201 Me,SiCN, 213 Michael reaction, 202 steric effects in, 201

Nucleophilic addition to 31,203- 244

a&tylide ions, 223 acid catalysis, 204,207,209,220,225 additionlelimination, 219 alcohols, 209 aldol reaction, 224

408 Index

Ion pairs (contd.) intimate, 91, 249, 291 solvation, 45, 57, 81, 390 solvent separated, 91

Ipso substitution, 161, 169 steric effects in, 162

Isocyanate intermediates, 49, 122 Isomer distribution, 158 Isomerisation, cis + tram, 315 Isoprene, 323 Isotope effects, kinetic, 46,83,139, 252,

288,295 Isotopic labels, 47

bromide, 141 carbon, 48, 108,233, 355 deuterium, 47, 117, 131, 174,216,

217,224,233,250,264,278,288 iodine, 89 monitoring, 48,89 nitrogen, 170 oxygen, 47,89,125, 127,189,207,239 scrambling of, 108,141,169 sulphur, 165

K, 35,359 k, 38, 359, 374 K,, 54, 65

AGe and, 58 K*, 65

AGe and, 66 Ketenes, 119 B-Keto-acids, decarboxylation, 286 Keto-enol tautomerism, 201,219,225

carbanions in, 278 catalysis of, 277 equilibrium and structure, 280,297 hydrogen bonding and, 281 mechanism of, 278 solvent and, 282

Ketones, halogenation, 295 bromination, 41,51, 76,297 electronic effects in, 2% enolisation in, 297 general acid catalysis, 297 general base catalysis, 76 orientation in, 2%, 297 rate of, 295,2%, 297

Ketoximes, Beckmann rearrangement, 123

Ketyls, 218 Kinetic acidity, 280 Kinetic control, 42, 151

addition to C=0, 235 addition to dienes, 195 Diels-Alder, 350

nitration, 43 protonation, 283

Kinetic data, interpretation, 40, 44, 78 Kinetic isotope effects, 46

carbon, 47 chlorine, 47 deuterium, 44,83,252,288,295 primary, 44,252,288,295 secondary, 83

Kinetics of reaction, 36 isotope effects in, 46 measurement of, 39,89 rate-limiting step in, 39

Knocking, 305 Knoevenagel reaction, 228 Kolbe electrolytic synthesis, 307 Kolbe-Schmidt reaction, 291

LaetPms, 126 Lactone intermediates, 94, 127, 228 Lateral overlap, orbitals, 9 Lead alkyls, 301

anti-knock, 305 thermolysis, 301, 304, 324

Leaving groups, 98,99, 127, 139,237 ability of, 98, 251 bromobenzene sulphonate ion, 375 cyanide ion, 232 ethanoate anion, 228 ethoxide ion, 229 hydride ion, l68 hydrogen bonding and, 252 hydroxyl ion, 225,253 in elimination, 247,251,253 internal, 100 nitrogen, 100,104,107,114, 121,123,

169,305 protonated, 103, 125 relative ability, 98, 251, 253 tosylate, 89,98,100,253 triflate, 98

Levelling effect, water, 55 Lewis acids, 29 Lewis bases, 29 Light absorption, colour and, 13 Lindlar catalyst, 191,223 Linear free energy relationships, 358-

395 Lithium

alkyls, 223, 238, 293 aryls, 223,233,293

Lithium aluminium hydride, 214 Localised orbitals, 6 Lone pairs, 10,72

in neighbouring groups, 94 protonated, 99,103

X Lossen rearrangement, 123 k 84

LUMO, 344

Magnetic moment, electronic, 308 Markownikov addition, 184 Mass spectrometry, 176 m, compound parameter, 390

diagnostic use of, 391 Mechanistic borderline, 91 Meerwein-Ponndorf reaction, 215 Meisenheimer complexes, 171 Mesomeric effect, 23, 154, 156, 172,238,

278 Meta (m)-directing groups, 150 Metal alkyls

carbonation, 284 thermolysis, 304 Wurtz reaction and, 289

Michael reaction, 200 Migration

origin, 116 terminus, 116 to electron-deficient C, 109, 110-119 to electron-deficient N, 122-126 to electron-deficient 0 , 127-129

Migratory aptitude, 114, 129 conformation of T.S. and, 118

Mixed SN1/SN2 pathway, 92 Models for T.S., 41,51,78,137,151,

194,254 Molecularity, 79 Molecular orbitals, 5,343 Molozonides, 193 Monomers, 321 Mustard gas, 96

Naphthalene, 17 nitration, 164 sulphonation, 164

N-brornosuccinimide, 327 Neighbouring group participation, 93-

96,181,377 Neopentyl rearrangements, 110 Newman projections, 7,235 Nitration, 31,45, 133-138

dilute HNO, in, 137 isotope effects in, 46 kinetics of, 134, 135 naphthalene, 164 nitronium Buoroborate in, 135 NO? in, 134

Nitrating mixture, 133 Nitrenes, 21, 122

carbonyl, l22 Nitriles, reactions, 244

Nitroalkanes acidity, 272, 280 addition to C=O, 226 tautomerism, 283

Nitrodealkylation, 162 Nitrodehalogenation, 162 Nitroeen, electron-deficient, migration

t;, l20 Nitroniurn ion, 45, 103,134 Nitrosating agents, 119 Nitrosation

phenol, 137 primary aliphatic amines, 107, 119 ~rimary aromatic amines, 120 secondary amines, 121 tertiary amines, 121

Nitrosoniurn ion, 120, 137 Nitro~otrialk~lammonium cation, 121 Nitrous acid, protonated, 120 N.m.r. spectroscopy, 18,48, 102, 106,

111, 126, 129, 159, 181,219 aromaticity and, 18 13c, 49,106, 111,393 carboxyl protonation and, 240 Grignard reagents and, 221 ozonolvsis and, 193, 194 ox and; 393 triphenylmethyl dimer, 44,301

N-nitroso comwunds, 121 Nodal

plane, 3,343 surface, 2

Nodes, 343 Non-bonded interaction, 7 Nucleophiles, 29

ambident, 97 Nucleophilic addition to =, 198

carbanions in, l99 cyanoethylation, 199 hydrogen cyanide, 199 methanol, 199 Michael reaction, 200

Nucleo~hilic addition to =m, 206

conjugate addition, 201 Grignard reagents, 201 Me,SiCN, 213 Michael reaction, 202 steric effects in, 201

Nucleophilic addition to 31,203- 244

a&tylide ions, 223 acid catalysis, 204,207,209,220,225 additionlelimination, 219 alcohols, 209 aldol reaction, 224

410 Index

Nucleophilic addition to C==O (contd.) ammonia derivs., 219 base catalysis, 204,207,212, 216, 226 benzoin condensation, 231 bisulphite anion, 207,213 Cannizzaro reaction, 216 carbanions, 221-234 Claisen ester condensation, 229 Claisen-Schmidt reaction, 226 conjugate, 200,213 cyanide ion, 212 Dieckmann reaction, 230 electronic effects in, 205,208,226 electrons, 217 Grignard reagents, 221,235 halide ion, 214 hydration, 207 hydride ion, 214 hydrogen bonding in, 204,209 in carboxylic derivs., 236-244 intermediates in, 50,219 intramolecular, 217,232 irreversible, 215, 222 Knoevenagel reaction, 228 Lewis acids in, 204,222 Meerwein-Ponndorf reaction, 215 Me3SiCN, 213 nitroalkanes, 226 Perkin reaction, 227 pH and, 204,208,219 protection, 211 rate-limiting step, 205,212,216,220 reversibility, 206,210,212, 224 size of nucleophile in, 207, 213 spectroscopy and, 50,219 stereoselectivity, 234 steric effects in, 205,213,222,243 Stobbe reaction, 228 thiols, 211 T.S. in, 205 Wittig reaction, 233

Nucleophilic catalysis, 99 Nucleophilicity, 96, 211

basicity and, 96 soft bases and, 96

Nucleophilic substitution, aliphatic, 31, 45.77-100

Aga catalysis, 97 ally1 halides, 85 ambident nucleophiles, 97 benzyl halides, 84,91 bridgehead halides, 86 bromomethane, 78 2-bromopropanoate, 94 l-bromotriptycene, 87 carbanions in, 100,288

charge distribution in T.S., 78, 80,83, 84

1,2-chlorohydrins, 94 2-chloro-2-methylpropane, 78 configuration in, 88,89,90,92,93,94 electronic effects in, 82, 83, 84 entering group and, 96 He catalysis, 99 I~ catalysis, 98 isotopic label (I) in, 89 kinetics of, 45, 77, 89 leaving group and, 98 list of reactions, 99 mechanistic borderline, 91 mechanistic changeover, 82,84,96 neighbouring group participation, 93 neopentyl halides, 86 rate1li&ting step, 78 SNl, 79, 90 S~2 ,78 ,87 , 93

solvation in, 45, 79, 80, 90, 91, 97 solvolysis, 80, 91 steric effects in, 82, 84,85,86, 109 stereochemistry of, 87-96 structure and, 82-87,90 tosylates, 89 triphenylmethyl halides, 84 v. elimination, 100,248, 260 vinvl halides. 85

~ u c l ~ o ~ h i l i c s"bstitution, aromatic, 167-177

activated aryl halides, 170 anionic intermediates, 168, 170, 171 aryne intermediates, 173 as additionlelimination, 172 as eliminationladdition, 175 deuterium exchange, 174 diazonium salts, 121, 169 ipso, 169 nitrobenzene, 168 pyridine, 168 steric inhibition of delocalisation, 173

Nylon-6, 126

Oleum, 140 Oppenauer oxidation, 216 Orbitals

anti-bonding, 6, 292 atomic, 1 axial overlap, 6 bonding, 6 degenerate, 3 delocalised, 13 dumb-bell, 3

Index 411

filled, l7 frontier, 344 HOMO, 344 hybridisation of, 4 lasral overlap, 9 lobes, 9 localised, 6 LUMO, 344 molecular, 5 nodal planes and, 1,343 overlap integral, 5, 342 P, 2 phase of, 342 A, 9,337 S*, 9, 337 S, 2 shape, 3 0, 6 U*, 6 size, 2 secondary interaction, 350 spl, 5 sp2, 5 sp3, 4 spatial orientation, 2, 3 symmetry, 342

Order of reaction, 39, 79 first, 39 mixed, 82,91 molecularity and, 79 second, 39

Organometallic compounds, structure, 221,276,293

Orthoesters acetals from, 210,289 hydrolysis, 75

Ortholpara (0-lp-) directing groups, 150,159 ratios, 159

Osmic esters, cyclic, 189 Osmium tetroxide, 189 Overlap

axial, 6 integral, 5,342 lateral, 9

Oxaphosphetanes, 233 Oximes

configuration, 124,220 formation, 219 rearrangement, 123

Oxygen diradical, 315 migration to electron-deficient, 127

Ozonides, 192 Ozonolysis, 192

stereochemistry, 193

Paramagnetism, 308 Paint, hardening, 328 Partial rate factors,f,, 156,159,333 Pauli principle, 2 Pericyclic reactions, 198,341 Perkin reaction, 227 Peroxide effect, 317 Peroxides

as initiators, 300, 317 heterolysis, 129, 306 homolysis, 129, 333 in ozonolysis, 193 photolysis, 304 rearrangement, l27 thermolysis, 304 trans-annular, 331

Peroxyacids, 190,330 Peroxy radicals, 315,328,337 Peroxy zwitterions, 193 Petroleum cracking, 112,305 Phase, orbital, 342 Phenanthrene, 17

Pschorr synthesis, 334 Phenol

acidity, 23,61,370 coupling, 334 diazo coupling, 147, 155 from cumene, 128 nitration, 137 oxidation, 334

Phenonium ion, 105,376 Phenylation, 332 Phenylnitromethane, tautomerism, 283 Phenyl radicals, 332 Phosphine oxides, 234 Phosphonium ylids, 233 Phosphoranes, 233 Phosphorus-oxygen bond, 233 Photochemical concerted reactions, 341,

346 1,3-hydrogen shifts, 354 1,7-hydrogen shifts, 354 2ne + 2ne, 349

Photochemical initiation, 300 Photo-dimerisation, 337 Photolysis, 303 Photo-oxidation, 330 Physical methods

analysis of products, 43,156,281 detection of intermediates, 50, 144,

171, 176,181,219,304,308 structure determination, 102, 106,

111, 134,193,221,240 n bond, 9, 178 n complexes, 131, 180, 184 n-deficient heterocycles, 165

410 Index

Nucleophilic addition to C==O (contd.) ammonia derivs., 219 base catalysis, 204,207,212, 216, 226 benzoin condensation, 231 bisulphite anion, 207,213 Cannizzaro reaction, 216 carbanions, 221-234 Claisen ester condensation, 229 Claisen-Schmidt reaction, 226 conjugate, 200,213 cyanide ion, 212 Dieckmann reaction, 230 electronic effects in, 205,208,226 electrons, 217 Grignard reagents, 221,235 halide ion, 214 hydration, 207 hydride ion, 214 hydrogen bonding in, 204,209 in carboxylic derivs., 236-244 intermediates in, 50,219 intramolecular, 217,232 irreversible, 215, 222 Knoevenagel reaction, 228 Lewis acids in, 204,222 Meerwein-Ponndorf reaction, 215 Me3SiCN, 213 nitroalkanes, 226 Perkin reaction, 227 pH and, 204,208,219 protection, 211 rate-limiting step, 205,212,216,220 reversibility, 206,210,212, 224 size of nucleophile in, 207, 213 spectroscopy and, 50,219 stereoselectivity, 234 steric effects in, 205,213,222,243 Stobbe reaction, 228 thiols, 211 T.S. in, 205 Wittig reaction, 233

Nucleophilic catalysis, 99 Nucleophilicity, 96, 211

basicity and, 96 soft bases and, 96

Nucleophilic substitution, aliphatic, 31, 45.77-100

Aga catalysis, 97 ally1 halides, 85 ambident nucleophiles, 97 benzyl halides, 84,91 bridgehead halides, 86 bromomethane, 78 2-bromopropanoate, 94 l-bromotriptycene, 87 carbanions in, 100,288

charge distribution in T.S., 78, 80,83, 84

1,2-chlorohydrins, 94 2-chloro-2-methylpropane, 78 configuration in, 88,89,90,92,93,94 electronic effects in, 82, 83, 84 entering group and, 96 He catalysis, 99 I~ catalysis, 98 isotopic label (I) in, 89 kinetics of, 45, 77, 89 leaving group and, 98 list of reactions, 99 mechanistic borderline, 91 mechanistic changeover, 82,84,96 neighbouring group participation, 93 neopentyl halides, 86 rate1li&ting step, 78 SNl, 79, 90 S~2 ,78 ,87 , 93

solvation in, 45, 79, 80, 90, 91, 97 solvolysis, 80, 91 steric effects in, 82, 84,85,86, 109 stereochemistry of, 87-96 structure and, 82-87,90 tosylates, 89 triphenylmethyl halides, 84 v. elimination, 100,248, 260 vinvl halides. 85

~ u c l ~ o ~ h i l i c s"bstitution, aromatic, 167-177

activated aryl halides, 170 anionic intermediates, 168, 170, 171 aryne intermediates, 173 as additionlelimination, 172 as eliminationladdition, 175 deuterium exchange, 174 diazonium salts, 121, 169 ipso, 169 nitrobenzene, 168 pyridine, 168 steric inhibition of delocalisation, 173

Nylon-6, 126

Oleum, 140 Oppenauer oxidation, 216 Orbitals

anti-bonding, 6, 292 atomic, 1 axial overlap, 6 bonding, 6 degenerate, 3 delocalised, 13 dumb-bell, 3

Index 411

filled, l7 frontier, 344 HOMO, 344 hybridisation of, 4 lasral overlap, 9 lobes, 9 localised, 6 LUMO, 344 molecular, 5 nodal planes and, 1,343 overlap integral, 5, 342 P, 2 phase of, 342 A, 9,337 S*, 9, 337 S, 2 shape, 3 0, 6 U*, 6 size, 2 secondary interaction, 350 spl, 5 sp2, 5 sp3, 4 spatial orientation, 2, 3 symmetry, 342

Order of reaction, 39, 79 first, 39 mixed, 82,91 molecularity and, 79 second, 39

Organometallic compounds, structure, 221,276,293

Orthoesters acetals from, 210,289 hydrolysis, 75

Ortholpara (0-lp-) directing groups, 150,159 ratios, 159

Osmic esters, cyclic, 189 Osmium tetroxide, 189 Overlap

axial, 6 integral, 5,342 lateral, 9

Oxaphosphetanes, 233 Oximes

configuration, 124,220 formation, 219 rearrangement, 123

Oxygen diradical, 315 migration to electron-deficient, 127

Ozonides, 192 Ozonolysis, 192

stereochemistry, 193

Paramagnetism, 308 Paint, hardening, 328 Partial rate factors,f,, 156,159,333 Pauli principle, 2 Pericyclic reactions, 198,341 Perkin reaction, 227 Peroxide effect, 317 Peroxides

as initiators, 300, 317 heterolysis, 129, 306 homolysis, 129, 333 in ozonolysis, 193 photolysis, 304 rearrangement, l27 thermolysis, 304 trans-annular, 331

Peroxyacids, 190,330 Peroxy radicals, 315,328,337 Peroxy zwitterions, 193 Petroleum cracking, 112,305 Phase, orbital, 342 Phenanthrene, 17

Pschorr synthesis, 334 Phenol

acidity, 23,61,370 coupling, 334 diazo coupling, 147, 155 from cumene, 128 nitration, 137 oxidation, 334

Phenonium ion, 105,376 Phenylation, 332 Phenylnitromethane, tautomerism, 283 Phenyl radicals, 332 Phosphine oxides, 234 Phosphonium ylids, 233 Phosphoranes, 233 Phosphorus-oxygen bond, 233 Photochemical concerted reactions, 341,

346 1,3-hydrogen shifts, 354 1,7-hydrogen shifts, 354 2ne + 2ne, 349

Photochemical initiation, 300 Photo-dimerisation, 337 Photolysis, 303 Photo-oxidation, 330 Physical methods

analysis of products, 43,156,281 detection of intermediates, 50, 144,

171, 176,181,219,304,308 structure determination, 102, 106,

111, 134,193,221,240 n bond, 9, 178 n complexes, 131, 180, 184 n-deficient heterocycles, 165

Zndex 413

n-excessive heterocycles, 166 Pinacolinic deamination, 113, 118 Pinacollpinacolone rearrangement, 113

migratory aptitude in, 114 Pinacols

formation, 218 rearrangement, l13

pK,, 54,270,362 temperature and, 64

P&, 65 P~B*, Plane trigonal hybridisation, 5 Polarisability, 24, % Polarisation, 22, 29 Polarised complexes, 108, 141, 144 Polar non-protic solvents, 81 Polyenes

hydrogen shifts in, 352 Polyisoprenes, 323 Polymerisation

anionic, 200,226 branching, 321 cationic, 189 chain length, 321 chain transfer, 321 coordination, 322 copolymerisation, 322 cross-linking, 323 induction period, 321 initiation, 321 propagation, 320 radical, 308, 320 stereochemistry, 322,323 termination, 320

Products, nature of, 43 Propane, rearrangement, 108 Protecting groups, 155,210,211,265

requirements, 211 Protodesilylation, 149,161 Protodesulphonylation, 140, 161 Proton transfer

catalysed, 74 to C=c, 103 to lone pairs, 103, 112, 116

Prototropy, 277 Pschorr reaction, 334 Pyridine

basicity, 72 delocalisation in, 18, 165 electrophilic substitution, 165 nucleophilic substitution, 168

Pyrolytic elimination, 267, 340 carbocationic character T.s., 269, 340 Cope, 268 chugaev, 268 Ei, 261

SYN, 267 Pyrrole

basicity, 73 electrophilic substitution, 166 protonation, 73

Quantum numbers principal, n, 2 spin, 2 subsidiary, l and m, 2

Quinuclidine basicity, 72 complex with Me,B, 28

RaeemisPtion, 89 deuterium exchange and, 288 in radical reactions, 326 in S,1, 90

Radical addition, 312-323 carbon tetrachloride, 320 halogens, 313 hydrogen bromide, 316 sulphenyl halides, 320 vinyl polymerisation, 320

Radical anions, 218 Radical rearrangements, 335 Radicals, 20,30,299-339

acyl, 306,330,335 addition to C=c, 313-323 alkoxyl, 303 alkyl, 301, 303,304, 324 allylic, 311, 325,327, 329 benzoyl, 330 benzylic, 311,316, 329 biradicals, 315, 330, 337 bridged, 310 chain reactions, 300,313, 314, 328 combustion and, 299 conformational equilibrium, 319 cycloheptatrienyl, 308 cyclohexadienyl, 331 detection, 308 dimerisation, 300, 305, 311, 313, 314,

320,332,334 l ,l-diphenyl-2-picrylhydrazyl, 301 disproportionation, 305,313, 320,332 e.s.r. spectroscopy and, 308 formation, 303 half-life, 301,305 halomethyl, 320 hetero, 302 hydroxyl, 306 in acyloxylation, 333 in aromatic substitution, 331, 334 in arylation, 332 in autoxidation, 306, 318,328

in Barton reaction, 337 in Gomberg reaction, 333 in halogenation, 323 in hydroxylation, 332 inhibitors, 300, 318, 321 initiators, 314, 321 in phenol oxidation, 334 in polymerisation, 308, 320 in Pschorr reaction, 334 oxygen and, 300 paramagnetic, 308 pentachloroethyl, 314 perbenzoate, 330 phenoxy, 302,334 peroxy, 315,328,337 polar effects in, 325 rearrangement, 325 shape, 309,326 solvent and, 309,324 stability, 302, 309, 312,324 stereoselectivity and, 318, 326, 333 terminators, 300,321 thiyl, 302, 319 trapping, 302 triphenylmethyl, 43,300,306,311

Radical substitution, 323-335 aromatic, 331 autoxidation, 328 halogenation, 323

Radiolysis, 304 Raman spectra, 134 Raney nickel catalyst, 212 Rate constant, k, 38, 39 Rate equation, 39

mixed order, 82,91 T.S. and, 41

Rate-limiting step, 39,40, 134, 148, 171, 381

Rate of reaction activation energy and, 37 catalysts and, 41 measurement of, 39 a and, 366 temperature and, 38

Reaction collisions in, 38 concerted, 341 energetics of, 33, 37 energy profile of, 37 heat of, 34 intermediates, 38,49 kinetics of, 36 molecularity, 79 order, 39,79 rate constant, 38 rate-limiting step, 39

types of, 30 Reaction constant, p, 363

attenuation of, 368 determination of, 363 effect of solvent on, 388 physical significance of, 367 rate-limiting step and, 368,381 reaction centre and, 368 reaction pathway and, 378 sign of, 368 values of, 364 variation with solvent, 388

Reaction mechanism, investigation, 43, 375

Reactive methylenes, 288 Reagents, classification, 28 Rearrangements, 30,32, 109-129,352-

357 alkanes, 108 alkenes, 112 allylic, 109 aryl, 128 Beckmann, l23 benzilic acid, 232 carbanions, 292 carbocations, 109-119 Claisen, 355 configuration in, 116, 123 conformation in, 115,118 Cope, 354 Curtius, l22 diazoamino comps., 148 diazoketones, 119 dienone-phenol, 115 Favorskii, 294 Hofmam, 122 hydroperoxides, l28 in Friedel-Crafts, 108, 142, 145, 163 intermolecular, 117, 143, 149,278 intramolecular, 116, 122, 126, 127,

279,355 Lossen, 122 migratory aptitude in, 114 neopentyl, 110 pinacol-pinacolone, 113 radical, 335 Schmidt, 122 sigmatropic, 352 stereochemistry of, 116,117,119 steric effects in, 115 Stevens, 293 Wagner-Meemein, 111 Wittig, 293 Wolff, 119

Redox reactions, 306 Reimer-Tiemann reaction, 290

Zndex 413

n-excessive heterocycles, 166 Pinacolinic deamination, 113, 118 Pinacollpinacolone rearrangement, 113

migratory aptitude in, 114 Pinacols

formation, 218 rearrangement, l13

pK,, 54,270,362 temperature and, 64

P&, 65 P~B*, Plane trigonal hybridisation, 5 Polarisability, 24, % Polarisation, 22, 29 Polarised complexes, 108, 141, 144 Polar non-protic solvents, 81 Polyenes

hydrogen shifts in, 352 Polyisoprenes, 323 Polymerisation

anionic, 200,226 branching, 321 cationic, 189 chain length, 321 chain transfer, 321 coordination, 322 copolymerisation, 322 cross-linking, 323 induction period, 321 initiation, 321 propagation, 320 radical, 308, 320 stereochemistry, 322,323 termination, 320

Products, nature of, 43 Propane, rearrangement, 108 Protecting groups, 155,210,211,265

requirements, 211 Protodesilylation, 149,161 Protodesulphonylation, 140, 161 Proton transfer

catalysed, 74 to C=c, 103 to lone pairs, 103, 112, 116

Prototropy, 277 Pschorr reaction, 334 Pyridine

basicity, 72 delocalisation in, 18, 165 electrophilic substitution, 165 nucleophilic substitution, 168

Pyrolytic elimination, 267, 340 carbocationic character T.s., 269, 340 Cope, 268 chugaev, 268 Ei, 261

SYN, 267 Pyrrole

basicity, 73 electrophilic substitution, 166 protonation, 73

Quantum numbers principal, n, 2 spin, 2 subsidiary, l and m, 2

Quinuclidine basicity, 72 complex with Me,B, 28

RaeemisPtion, 89 deuterium exchange and, 288 in radical reactions, 326 in S,1, 90

Radical addition, 312-323 carbon tetrachloride, 320 halogens, 313 hydrogen bromide, 316 sulphenyl halides, 320 vinyl polymerisation, 320

Radical anions, 218 Radical rearrangements, 335 Radicals, 20,30,299-339

acyl, 306,330,335 addition to C=c, 313-323 alkoxyl, 303 alkyl, 301, 303,304, 324 allylic, 311, 325,327, 329 benzoyl, 330 benzylic, 311,316, 329 biradicals, 315, 330, 337 bridged, 310 chain reactions, 300,313, 314, 328 combustion and, 299 conformational equilibrium, 319 cycloheptatrienyl, 308 cyclohexadienyl, 331 detection, 308 dimerisation, 300, 305, 311, 313, 314,

320,332,334 l ,l-diphenyl-2-picrylhydrazyl, 301 disproportionation, 305,313, 320,332 e.s.r. spectroscopy and, 308 formation, 303 half-life, 301,305 halomethyl, 320 hetero, 302 hydroxyl, 306 in acyloxylation, 333 in aromatic substitution, 331, 334 in arylation, 332 in autoxidation, 306, 318,328

in Barton reaction, 337 in Gomberg reaction, 333 in halogenation, 323 in hydroxylation, 332 inhibitors, 300, 318, 321 initiators, 314, 321 in phenol oxidation, 334 in polymerisation, 308, 320 in Pschorr reaction, 334 oxygen and, 300 paramagnetic, 308 pentachloroethyl, 314 perbenzoate, 330 phenoxy, 302,334 peroxy, 315,328,337 polar effects in, 325 rearrangement, 325 shape, 309,326 solvent and, 309,324 stability, 302, 309, 312,324 stereoselectivity and, 318, 326, 333 terminators, 300,321 thiyl, 302, 319 trapping, 302 triphenylmethyl, 43,300,306,311

Radical substitution, 323-335 aromatic, 331 autoxidation, 328 halogenation, 323

Radiolysis, 304 Raman spectra, 134 Raney nickel catalyst, 212 Rate constant, k, 38, 39 Rate equation, 39

mixed order, 82,91 T.S. and, 41

Rate-limiting step, 39,40, 134, 148, 171, 381

Rate of reaction activation energy and, 37 catalysts and, 41 measurement of, 39 a and, 366 temperature and, 38

Reaction collisions in, 38 concerted, 341 energetics of, 33, 37 energy profile of, 37 heat of, 34 intermediates, 38,49 kinetics of, 36 molecularity, 79 order, 39,79 rate constant, 38 rate-limiting step, 39

types of, 30 Reaction constant, p, 363

attenuation of, 368 determination of, 363 effect of solvent on, 388 physical significance of, 367 rate-limiting step and, 368,381 reaction centre and, 368 reaction pathway and, 378 sign of, 368 values of, 364 variation with solvent, 388

Reaction mechanism, investigation, 43, 375

Reactive methylenes, 288 Reagents, classification, 28 Rearrangements, 30,32, 109-129,352-

357 alkanes, 108 alkenes, 112 allylic, 109 aryl, 128 Beckmann, l23 benzilic acid, 232 carbanions, 292 carbocations, 109-119 Claisen, 355 configuration in, 116, 123 conformation in, 115,118 Cope, 354 Curtius, l22 diazoamino comps., 148 diazoketones, 119 dienone-phenol, 115 Favorskii, 294 Hofmam, 122 hydroperoxides, l28 in Friedel-Crafts, 108, 142, 145, 163 intermolecular, 117, 143, 149,278 intramolecular, 116, 122, 126, 127,

279,355 Lossen, 122 migratory aptitude in, 114 neopentyl, 110 pinacol-pinacolone, 113 radical, 335 Schmidt, 122 sigmatropic, 352 stereochemistry of, 116,117,119 steric effects in, 115 Stevens, 293 Wagner-Meemein, 111 Wittig, 293 Wolff, 119

Redox reactions, 306 Reimer-Tiemann reaction, 290

414 Index Zndex 415

Relative configuration, determination, 88

Resonance energy, 17 Retro Diels-Alder reaction, 351 Retro pinacol rearrangement, 115 P, 363 p*, 385 Rotational entropy, 36 Rotation frequency, 8 Rubber

natural, 323 perishing of, 328 synthetic, 189,322 vulcanisation, 323

Sandmeyer reaction, 306 Sandwich comoounds. 275 Sawhorse projections, 7 Saytzev elimination, 249, 256 Schiff bases, 221 Schmidt rearrangement, 122 Selectivity, 156, 169, 326 a, 362 a-, 370 a+, 372 a;, 385 o bonds, 6 U complexes, 41, 131 Sigmatropic rearrangements, 352-357

antarafacial, 353 carbon shifts, 354 hydrogen shifts, 352 orbital symmetry in, 352 photochemical, 354 suprafacial, 353 thermal, 353

Silicon-oxygen bond, 213 SE1 pathway, 288,295 SN1 pathway, 79,370,389 SN2 pathway, 78,376 SN2' pathway, 110 SN2 (aromatic) pathway, 170 SNi pathway, 92 Sodium borohydride, 215 Soft bases, 96 Solvation, 45,56,79,253,299,388

H-bonded, 57,67,81,253 AS^ and, 58,60,63,66 polar non-protic. 81. 173.252

Solvatochromic shifts, 391 Solvent

bipolar non-protic, 81,98, 173,252 effect of, 45,80, 161,252,260,388 E, and, 391 ionising power, 390 ion-solvating ability, 80,260, 390

parameter, Y, 389 Solvent separated ion pair, 90 Solvolysis, 80, 91, 109, 389 Specific acid catalysis, 74,209 Specific base catalysis, 75 Spectrosco ic correlations, 392 P a, and ' C n.m.r., 393 a, and 'H n.m.r., 393 a, and i.r. shifts, 392

Spin, electronic, paired, 2 Stabilisation energy, 13 Stability, thermodynamic, 12 Staggered conformation, 7 Standing waves, electronic, 342 Stereochemical criteria, 51 Stereoselectivity, 52

in acetolysis, 377 in addition to -, 51,180, 182,318 in addition to C==0,234 in Beckmann, 124 in concerted reactions, 341 in Diels-Alder, 198,349 in elimination, 253, 264, 267 in ozonolysis, 193 in rearrangements, 118

Steric effects, 26 crowding, 27,115,235,301,350 delocalisation and, 26,71, 172 in acidity, 58 in addition to C=C, 181 in addition to 205,235 in aromatic substitution, 152, 159,

162, 165 in diazo coupling, 27 in elimination, 261 in ester hydrolysis, 241 in rearrangements, 115 non-bonded interaction, 7

Steric hindrance, 27,79, 110, 159, 162, 222,235,243,301,312,356

Steric parameters, 386 E,, 386 6, 387

Sterigrnatocystin, 48 Stevens rearrangements, 293 Stobbe reaction, 228 Substituent constant, a, 362

'constancy' of, 368,372 determination of, 363 physical significance of, 364 pK, and, 362 polar effects and, 366 sign of, 364 spectroscopic shifts and, 392 values of, 363

Substituent effects, 150, 388

Substitution electrophilic, aromatic, 41, 130-167 nucleophilic. aliphatic. 31.77-100 nucleophilic; aromatic; 167-177 radical, 323-335

Sulphenyl compounds, 320 Sulphonation, 29, 140, 164 Sulphonium salts, 95, 99

cyclic, 95 elimination from, 258

Sulphur trioxide, in sulphonation, 140 Sulphuryl chloride, in chlorination, 327 Super acids, 102, 129, 181 Suprafacial shifts, 353 Symmetry controlled reactions, 340-357

activation parameters, 342 'allowed', 348 antarafacial shifts, 353 Claisen rearrangement, 355 concerted v. stepwise, 342,351 conrotation, 345 Cope rearrangement, 354 cycloaddition, 348 Diels-Alder reaction, 349 disrotation, 345 electrocyclic, 344 'forbidden', 348 residual bonding in, 342 secondary orbital interaction, 350 sigmatropic rearrangements, 352 suprafacial shifts, 353

Symmetry, orbital, 344 Synperiplanar conformation, 253,269

Taft equation, 384 amide hydrolysis and, 388 derivation of, 386 6 parameter in, 387 E, parameter in, 386 ester hydrolysis and, 384 polar effects in, 385 p* in, 385 a& in, 385 standard substituent in, 385

Tautomerism, 277 catalysis of, 277 equilibrium and structure, 280 intermolecular, 278 intramolecular, 278,279 keto-enol, 201,219,225,277 mechanisms of, 278 nitroalkanes, 277,283 rate and structure, 279 rate-limiting step, 279

Terminators, 300,320

Tetraalkylammonium salts basicity, 67 elimination from, 254,256

Tetrahedral hybridisation, 4 Tetrahedral intermediates. 236. 361 , .

isolation, 237 Thermal concerted reactions, 341

Claisen rearrangement, 355 Cope rearrangement, 354 1,Shydrogen shifts, 353 1,7-hydrogen shifts, 354 4xe + 2xe, 348

Thermodynamic control, 43, 163 addition to C==0,235 addition to dienes, 195 Diels-Alder , 350 Friedel-Crafts, l63 napthalene sulphonation, 43, 164 nitroalkane formation, 283

Thermodynamics, second law, 34 Thermodynamic stability, 12

alkenes, 26, 249 benzene, 15 delocalisation and, 26 dienes, 12 hyperconjugation and, 26 keto-enol forms, 282

Thiazolium ylids, 232 Thioacetals, 211

desulphurisation, 212 Thiols, addition to C==O, 211 Thionyl chloride, in chlorination, 92 Through-conjugation, 368

r and, 373 a and, 370 a+ and, 372,393

Transesterification, 239 Transition state, 24, 38

bridged, 118, 129,292,335 composition of, 41 conformation and, 118,235 crowding in, 27,83, 86, 183,206,235,

259,385 cyclic, 216,222,254,268,287, 352,

356 energy level of, 40, 137,235,283 models for, 41,49, 137, 151 orbital interaction in, 350 organisation in, 39 residual bonding in, 342 solvation of, 253 variable, 92,256,257

Translational entropy, 35,58,239,241 Transoid conformation, 197 Trapping of intermediates

arynes, 176

414 Index Zndex 415

Relative configuration, determination, 88

Resonance energy, 17 Retro Diels-Alder reaction, 351 Retro pinacol rearrangement, 115 P, 363 p*, 385 Rotational entropy, 36 Rotation frequency, 8 Rubber

natural, 323 perishing of, 328 synthetic, 189,322 vulcanisation, 323

Sandmeyer reaction, 306 Sandwich comoounds. 275 Sawhorse projections, 7 Saytzev elimination, 249, 256 Schiff bases, 221 Schmidt rearrangement, 122 Selectivity, 156, 169, 326 a, 362 a-, 370 a+, 372 a;, 385 o bonds, 6 U complexes, 41, 131 Sigmatropic rearrangements, 352-357

antarafacial, 353 carbon shifts, 354 hydrogen shifts, 352 orbital symmetry in, 352 photochemical, 354 suprafacial, 353 thermal, 353

Silicon-oxygen bond, 213 SE1 pathway, 288,295 SN1 pathway, 79,370,389 SN2 pathway, 78,376 SN2' pathway, 110 SN2 (aromatic) pathway, 170 SNi pathway, 92 Sodium borohydride, 215 Soft bases, 96 Solvation, 45,56,79,253,299,388

H-bonded, 57,67,81,253 AS^ and, 58,60,63,66 polar non-protic. 81. 173.252

Solvatochromic shifts, 391 Solvent

bipolar non-protic, 81,98, 173,252 effect of, 45,80, 161,252,260,388 E, and, 391 ionising power, 390 ion-solvating ability, 80,260, 390

parameter, Y, 389 Solvent separated ion pair, 90 Solvolysis, 80, 91, 109, 389 Specific acid catalysis, 74,209 Specific base catalysis, 75 Spectrosco ic correlations, 392 P a, and ' C n.m.r., 393 a, and 'H n.m.r., 393 a, and i.r. shifts, 392

Spin, electronic, paired, 2 Stabilisation energy, 13 Stability, thermodynamic, 12 Staggered conformation, 7 Standing waves, electronic, 342 Stereochemical criteria, 51 Stereoselectivity, 52

in acetolysis, 377 in addition to -, 51,180, 182,318 in addition to C==0,234 in Beckmann, 124 in concerted reactions, 341 in Diels-Alder, 198,349 in elimination, 253, 264, 267 in ozonolysis, 193 in rearrangements, 118

Steric effects, 26 crowding, 27,115,235,301,350 delocalisation and, 26,71, 172 in acidity, 58 in addition to C=C, 181 in addition to 205,235 in aromatic substitution, 152, 159,

162, 165 in diazo coupling, 27 in elimination, 261 in ester hydrolysis, 241 in rearrangements, 115 non-bonded interaction, 7

Steric hindrance, 27,79, 110, 159, 162, 222,235,243,301,312,356

Steric parameters, 386 E,, 386 6, 387

Sterigrnatocystin, 48 Stevens rearrangements, 293 Stobbe reaction, 228 Substituent constant, a, 362

'constancy' of, 368,372 determination of, 363 physical significance of, 364 pK, and, 362 polar effects and, 366 sign of, 364 spectroscopic shifts and, 392 values of, 363

Substituent effects, 150, 388

Substitution electrophilic, aromatic, 41, 130-167 nucleophilic. aliphatic. 31.77-100 nucleophilic; aromatic; 167-177 radical, 323-335

Sulphenyl compounds, 320 Sulphonation, 29, 140, 164 Sulphonium salts, 95, 99

cyclic, 95 elimination from, 258

Sulphur trioxide, in sulphonation, 140 Sulphuryl chloride, in chlorination, 327 Super acids, 102, 129, 181 Suprafacial shifts, 353 Symmetry controlled reactions, 340-357

activation parameters, 342 'allowed', 348 antarafacial shifts, 353 Claisen rearrangement, 355 concerted v. stepwise, 342,351 conrotation, 345 Cope rearrangement, 354 cycloaddition, 348 Diels-Alder reaction, 349 disrotation, 345 electrocyclic, 344 'forbidden', 348 residual bonding in, 342 secondary orbital interaction, 350 sigmatropic rearrangements, 352 suprafacial shifts, 353

Symmetry, orbital, 344 Synperiplanar conformation, 253,269

Taft equation, 384 amide hydrolysis and, 388 derivation of, 386 6 parameter in, 387 E, parameter in, 386 ester hydrolysis and, 384 polar effects in, 385 p* in, 385 a& in, 385 standard substituent in, 385

Tautomerism, 277 catalysis of, 277 equilibrium and structure, 280 intermolecular, 278 intramolecular, 278,279 keto-enol, 201,219,225,277 mechanisms of, 278 nitroalkanes, 277,283 rate and structure, 279 rate-limiting step, 279

Terminators, 300,320

Tetraalkylammonium salts basicity, 67 elimination from, 254,256

Tetrahedral hybridisation, 4 Tetrahedral intermediates. 236. 361 , .

isolation, 237 Thermal concerted reactions, 341

Claisen rearrangement, 355 Cope rearrangement, 354 1,Shydrogen shifts, 353 1,7-hydrogen shifts, 354 4xe + 2xe, 348

Thermodynamic control, 43, 163 addition to C==0,235 addition to dienes, 195 Diels-Alder , 350 Friedel-Crafts, l63 napthalene sulphonation, 43, 164 nitroalkane formation, 283

Thermodynamics, second law, 34 Thermodynamic stability, 12

alkenes, 26, 249 benzene, 15 delocalisation and, 26 dienes, 12 hyperconjugation and, 26 keto-enol forms, 282

Thiazolium ylids, 232 Thioacetals, 211

desulphurisation, 212 Thiols, addition to C==O, 211 Thionyl chloride, in chlorination, 92 Through-conjugation, 368

r and, 373 a and, 370 a+ and, 372,393

Transesterification, 239 Transition state, 24, 38

bridged, 118, 129,292,335 composition of, 41 conformation and, 118,235 crowding in, 27,83, 86, 183,206,235,

259,385 cyclic, 216,222,254,268,287, 352,

356 energy level of, 40, 137,235,283 models for, 41,49, 137, 151 orbital interaction in, 350 organisation in, 39 residual bonding in, 342 solvation of, 253 variable, 92,256,257

Translational entropy, 35,58,239,241 Transoid conformation, 197 Trapping of intermediates

arynes, 176

'V'

416 Index

Trapping of intermediates (contd.) carbenes, 50,267 dienones, 356 internal, 266 peroxynvitterions, 193

Trichloromethane hydrolysis, 42,267 Triphenylmethane

acidity, 271 carbanion from, 271,272 radical from, 43,300

Triphenylmethyl cation, 84, 87, 102, 103,381

reduction, 306 Triphenylmethyl peroxide, 300

rearrangement, 336 Triphenylmethyl radical, 43, 300

dimer, 44,301,311 shape, 311

Tropylium cation, 18, 104, 106 stability, 106

Tschitschibabin reaction, 168

Ultra-violet absorption, 13, 132,218 Umpolung, 21 1 Unsaturated acids

L$-, from Perkin reaction, 227 By-, synthesis, 234

Unsaturated carbonyl compounds, cub-, addition to, 200 formation of. 251

Van der Wads radii, 8 Vibrational modes, 342 Vinyl ethers, polymerisation, 189 Vinyl polymerisation, 320

branching in, 321 chain length in, 321 coordination, 322 induction period in, 321

initiation, 320, 321 propagation, 320 termination, 320,321

Vulcanisation, 323

Wngner-Meerwein rearrangements, 11 1 Water

addition to -, 187 addition to &---Cl, 207 autolysis of, 54 ion solvation and, 57,58,60 levelling effect in, 55 polarisability, 57

Wave amplitude, 343 Wave functions, 2,342 Wave nodes, 343 Wheland intermediates, 41, 131, 151 Wittig reaction, 233 Wittig rearrangement, 293 Wolff rearrangement, 119 Woodward-Hoffmam rules, 344 Wurtz reaction, 289

Xanthates, pyrolysis, 268 X-ray crystallography

ethanoate anion, 19 1

Grignard reagents, 221 Meisenheimer complexes, 171 triphenylmethyl radicals, 311

Ylids, 232,233,287 Y, solvent parameter, 389

values of, 390 Yukawa-Tsuno equation, 372

parameter, r, and, 373

Zinc alkyls, 223 Zwitterions, 94, 176

diazoanthranilate anion, 176 peroxy, 193

Notes

'V'

416 Index

Trapping of intermediates (contd.) carbenes, 50,267 dienones, 356 internal, 266 peroxynvitterions, 193

Trichloromethane hydrolysis, 42,267 Triphenylmethane

acidity, 271 carbanion from, 271,272 radical from, 43,300

Triphenylmethyl cation, 84, 87, 102, 103,381

reduction, 306 Triphenylmethyl peroxide, 300

rearrangement, 336 Triphenylmethyl radical, 43, 300

dimer, 44,301,311 shape, 311

Tropylium cation, 18, 104, 106 stability, 106

Tschitschibabin reaction, 168

Ultra-violet absorption, 13, 132,218 Umpolung, 21 1 Unsaturated acids

L$-, from Perkin reaction, 227 By-, synthesis, 234

Unsaturated carbonyl compounds, cub-, addition to, 200 formation of. 251

Van der Wads radii, 8 Vibrational modes, 342 Vinyl ethers, polymerisation, 189 Vinyl polymerisation, 320

branching in, 321 chain length in, 321 coordination, 322 induction period in, 321

initiation, 320, 321 propagation, 320 termination, 320,321

Vulcanisation, 323

Wngner-Meerwein rearrangements, 11 1 Water

addition to -, 187 addition to &---Cl, 207 autolysis of, 54 ion solvation and, 57,58,60 levelling effect in, 55 polarisability, 57

Wave amplitude, 343 Wave functions, 2,342 Wave nodes, 343 Wheland intermediates, 41, 131, 151 Wittig reaction, 233 Wittig rearrangement, 293 Wolff rearrangement, 119 Woodward-Hoffmam rules, 344 Wurtz reaction, 289

Xanthates, pyrolysis, 268 X-ray crystallography

ethanoate anion, 19 1

Grignard reagents, 221 Meisenheimer complexes, 171 triphenylmethyl radicals, 311

Ylids, 232,233,287 Y, solvent parameter, 389

values of, 390 Yukawa-Tsuno equation, 372

parameter, r, and, 373

Zinc alkyls, 223 Zwitterions, 94, 176

diazoanthranilate anion, 176 peroxy, 193

Notes

Contents*

Page

Foreword by Professor Lord Todd, O.M., P.P.R.S. ixPreface to sixth edition xi

1 Structure, reactivity, and mechanism 1

2 Energetics, kinetics, and the investigation of mechanism 33

3 The strengths of acids and bases 53

4 Nucleophilic substitution at a saturated carbon atom 77

5 Carbocations, electron-deficient N and O atoms and their 101reactions

6 Electrophilic and nucleophilic substitution in aromatic 130systems

7 Electrophilic and nucleophilic addition to C=C 178

8 Nucleophilic addition to C=O 203

9 Elimination reactions 246

10 Carbanions and their reactions 270

11 Radicals and their reactions 299

12 Symmetry controlled reactions 340

13 Linear free energy relationships 358

Select bibliography 396

Index 399